Stable and compatible polymer blends

ABSTRACT

The present invention pertains to products and processes relating to compatible polymer blends comprising at least one sulfonated polymer and at least one non-sulfonated polymer. The sulfonated polymers may be produced using a number of sulfonating agents including a coordination complex of sulfur trioxide. The polymeric blended materials described herein are useful in a variety of applications, including as coatings for medical devices, protective clothing and fabric, laboratory equipment, vascular stents and shunts, absorbent materials and separation membranes, three-dimensional constructs, devices, and other uses.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.60/937,195, filed 26 Jun. 2007, which is incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

The subject matter disclosed herein relates to blended materialscomprising sulfonated polymers (to include, for example, macromolecules,copolymers), and other polymeric compounds. Certain aspects relate toarticles of manufacture composed of the blended materials disclosedherein. In other particular aspects, the blended polymeric materials maybe incorporated as components in medical devices, medical instruments,vascular stents and shunts, clothing, fabric and other garments, spunfibers, woven or knit fabrics, thread, or yarn, other consumer products,moisture transfer membranes and their corresponding applications,including heat and/or fluid transfer membranes, moisture and/or heattransfer coatings, three-dimensional constructs, devices, as well asother applications.

BACKGROUND OF THE INVENTION

In the plastics industry it has been recognized that blending ofdifferent polymers can result in a composition that has properties thatare superior to those of each individual component. However, one of thelimitations of blending polymeric materials is that most polymerstructures are immiscible (e.g., incompatible) with other (structurallydifferent) polymers and when combined, the individual materials formphases that result in a product that does not have superior propertiesrelative to the individual components.

Specifically, immiscible polymer blends are not thermodynamicallystable. In addition, the post-mixing processing such as molding orannealing, can affect the blend morphology and reduce or eliminate anybenefits of blending. In order to overcome this, an additive is oftencombined with the polymeric blended materials.

In other instances, when two structures are joined together in block orgraft copolymer structures, the polymers oftentimes separate into phasesat a microscopic scale. When the constituents of the separate phases arecovalently linked to the polymer backbone, gross separation iseliminated and it is easier to produce compatible polymers, particularlyblock and graft copolymers. In block polymers, this micro-phaseseparation can result in improved material properties.

The sulfonated polymers described herein may be sulfonated by anyvariety of methods, including but net limited to, the specific exemplarysulfonation methods described herein. Sulfonation generally refers to anorganic chemical reaction that leads to the formation of a carbon-sulfurbond. When the reacting compound contains an aromatic ring, sulfonationat the aromatic ring by the reactive (sulfonating) compound usuallyoccurs by replacing a hydrogen atom on the aromatic ring by a sulfonicacid residue functional group by means of an electrophilic aromaticsubstitution reaction. However, with particular compounds, such asphenylalkanoic acids, sulfonation may occur on the carbon adjacent tothe carboxyl group, rather than on the aromatic ring. In contrast toaromatic nitration or other electrophilic aromatic substitutions,aromatic sulfonation is reversible.

Sulfonation of aromatic compounds utilizing sulfur trioxide, sulfuricacid, chlorosulfonic acid, or acetyl sulfate as the sulfonating agenthave been accomplished in the past with varying degrees of success.(Gilbert, Chem. Rev. 62: 549-589 (1962); German Patent No. DE 580,366).The processes can be expensive, difficult, and oftentimes results inincomplete sulfonation of the compound, especially for large molecularweight oligomers or polymers. (Gilbert, supra).

Moreover, the technique of using sulfur trioxide as the sulfonatingagent results in the generation of considerable amounts of undesiredside-products during the course of the sulfonation reaction andsubsequent work-up due to the high reactivity of the sulfur trioxide.The sulfonation side-products are frequently difficult to remove and maycontaminate the final sulfonated polymer product. (Gilbert, supra).

Thus, existing methods that describe using sulfur trioxide as asulfonating reagent to sulfonate compounds have resulted in non-uniform,incomplete sulfonation, and a high rate of formation of undesirableside-products. Further, sulfonation reactions utilizing sulfur trioxideand other reagents have, in some cases, resulted in limited ability tocreate sulfonated products, particularly with respect to sulfonatinglarge molecular polymers. Moreover, excess sulfuric acid and acetic acidthat result from the use of acetyl sulfate can only be removed by way ofan elaborate, and expensive, absorption or extraction cleaning processesor other means. Furthermore, the use of sulfuric acid introduces waterinto the reaction, which can alter the ability of the reactioncomponents to effectively solvate the polymer target. The introductionof water into the reaction through the use of sulfuric acid alsoprohibits sulfonating polymers with labile, or hydrolytically unstable,functional groups or moieties.

Sulfonated block copolymers have been produced by traditionalsulfonation. See, for example, U.S. Pat. No. 3,577,357. The resultingcopolymer was characterized as having the general configurationA-B-(B-A) 1-5, wherein each A is a non-elastomeric sulfonated monovinylarene polymer block and each B is a substantially saturated elastomericalpha-olefin polymer block, said block copolymer being sulfonated to anextent sufficient to provide at least 1% by weight of sulfur in thetotal polymer and up to one sulfonated constituent for each monovinylarene unit. The sulfonated polymers could be used in their producedform, or in their acid, alkali metal salt, or ammonium salt (includingcomplex amine) forms.

The sulfonation of unsaturated styrene-diene block copolymers has alsobeen attempted. See, for example, U.S. Pat. No. 3,642,953. In thisparticular example, polystyrene-polyisoprene-polystyrene was sulfonatedusing chlorosulfonic acid in diethyl ether. However, the sulfonic acidfunctionality incorporated into the polymer promotes oxidation, and theresidual alkene (C═C) sites left in the polymer backbone are prone torapid oxidation, restricting the utility of these polymers. Thus, themembranes produced with these polymers were found to be weak and couldnot be stabilized to make them practical for shaping or forming.

Similarly, in other examples, sulfonation of a t-butylstyrene/isoprenerandom copolymer and styrene/butadiene copolymer has been performed, butthe products are prone to oxidative degradation, and lack flexibility tobe formed or shaped. See, for example, U.S. Pat. Nos. 3,870,841 and6,110,616. Finally, a blend of an aliphatic hydrocarbon oil and afunctionalized, selectively hydrogenated block copolymer to which hasbeen grafted sulfonic functional groups has been prepared. See U.S. Pat.No. 5,516,831.

There is, therefore, a need in the art for novel and effective methodsfor the improvement of processing, mechanical properties, anddimensional stability of sulfonated polymers, and blended materialscomprising sulfonated polymers (to include, macromolecules, copolymers)

SUMMARY OF EXEMPLARY ASPECTS OF THE INVENTION

Particular aspects provide a polymeric material that is water insolubleand comprises at least one sulfonated aryl-containing copolymer and atleast one thermoplastic or thermosetting non-sulfonated homopolymer orcopolymer selected from the group consisting of a polyurethane, asegmented polyurethane, a poly(ether urethane), a poly(carbonateurethane), a poly(siloxy urethane), a polyurethane urea, anarylene-vinyl containing block copolymer, a polysiloxane, a polyamide, apolyurethane urea, a polyketone, a polyester, a poly(ether-ester), apolyanhydride, a polyamine, a poly(ortho ester), a polyacrylate, apolyalkylene, a polycarbonate, a poly(carbonate urethane) afluoropolymer, a polysulfone, carbohydrate polymers, a polypeptide, apolyphosphazine, a polyether, a poly(ether sulfone), apoly(vinylalcohol), poly(ethylene-co-vinyl acetate),poly(ethylene-co-vinyl alcohol), a poly(epoxide)-polyamine curingsystem, and an acrylate, wherein said sulfonated aryl-containingcopolymer is at least 20-80 mol % sulfonated. In certain embodiments,the sulfonated copolymer comprises al least one block copolymercomprising at least two polymer end blocks (A) and at least one polymerinterior block (B) wherein each (A) block is resistant to sulfonationand each (B) block is susceptible to sulfonation. In particular aspects,the sulfonated copolymer comprises an arylene-vinyl containing copolymerprepared by at least one of free radical polymerization, a coordinationcatalyst-based polymerization, a metallocene-based polymerization,condensation polymerization, ring-opening polymerization, reaction(step-growth) polymerization, and anionic polymerization or cationicpolymerization. In certain embodiments, the polymeric material furthercomprises a hydrogenated or saturated central block. In certain aspects,said (A) and (B) blocks contain no significant level of olefinicunsaturation and each (A) block has an average molecular weight ofbetween 1,000 and 60,000 and each (B) block has an average molecularweight of between 2,000 and 300,000. In particular embodiments, each (A)block comprises one or more polymerized segments selected from the groupconsisting of para-substituted styrene monomers, ethylene, alpha olefinsof 3 to 18 carbon atoms, 1,3-cyclodiene monomers, monomers of conjugateddienes having a vinyl content less than 35 mol percent prior tohydrogenation, acrylic esters, methacrylic esters, and mixtures thereof.In particular aspects, said para-substituted styrene monomers areselected from the group consisting of para-methylstyrene,para-ethylstyrene, para-n-proplystyrene, para-isopropylstyrene,para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene,para-t-butylstyrene, para-decylstyrene isomers, and para-dodecylstyreneisomers. In particular embodiments, any (A) block comprises polymerizedethylene or hydrogenated polymers of a conjugated acyclic diene and hasa melting point of greater than 50° C. In certain aspects, each (B)block comprises one or more polymerized segments selected from the groupconsisting of alkylene monomers, vinyl aromatic monomers, unsubstitutedstyrene monomers, ortho-substituted styrene monomers, meta-substitutedstyrene monomers, alpha-methylstyrene, 1,1-diphenylethylene,1,2-diphenylethylene, and mixtures thereof. In particular embodiments,said alkylene monomers are selected from the group consisting ofvariations of isobutylene, methyl cyclohexene, methylcyclopentene, and1-methyl, 1-ethyl ethane or higher alkyl derivatives thereof. Inparticular aspects, each (B) block is sulfonated to the extent of 10 to100 mol %, based on the units of arylene vinyl monomer in said (B)blocks. In particular embodiments, the mol % of arylene vinyl monomerswhich are unsubstituted styrene monomers, ortho-substituted styrenemonomers, meta-substituted styrene monomers, alpha-methylstyrene,1,1-diphenylethylene and 1,2-diphenylethylene in each (B) block isbetween 10 mol % and 100 mol %. In certain aspects, said sulfonatedcopolymer comprises a triblock copolymer wherein the (B) blocks comprisearylene-vinyl polymer segments and the (A) blocks comprise diene polymersegments. In certain embodiments, said (B) blocks are susceptible tosulfonation and said (A) blocks are resistant to sulfonation.

In particular embodiments, said sulfonated copolymer comprises a randomblock copolymer, a triblock copolymer, or a pseudo-random blockcopolymer in which the end blocks comprise arylene-vinyl polymer and thecentral blocks comprise at least one monoalkene polymer segment. Incertain aspects, said monoalkene polymer segment comprises at least fourcarbon atoms. In certain embodiments, said sulfonated copolymercomprises an aryl-containing condensation copolymer. In particularaspects, said condensation copolymer comprises a copolymer selected fromthe group consisting of polyurethane, polyamide, polyester,polysiloxane, and polycarbonate. In certain aspects, said sulfonatedcopolymer comprises a pseudo-random block copolymer or a random blockcopolymer in which the end blocks are comprised of arylene-vinyl polymerand the central block is comprised of a diene polymer comprising repeatunits of at least four carbon atoms. In certain embodiments, saidsulfonated copolymer comprises a random copolymer comprising anarylene-vinyl monomer and a non-arylene vinyl comonomer.

In particular aspects, said sulfonated copolymer is selected from thegroup consisting of polyethersulfone, polyetherketone, polystyrenemethylmethacrylate, polydioxanone, polylactides, polyglycolides,lactide-glycolide copolymers, and polyesters including terephthalates.In certain embodiments, said sulfonated copolymer comprises a generalconfiguration of A-D-B-D-A, A-B-D-B-A, (A-D-B)_(n)X, (A-B-D)_(n)X, ormixtures thereof, wherein n is an integer from about 2 to about 30, andX is coupling agent residue wherein each (A) block and each (D) block isresistant to sulfonation and each (B) block is susceptible tosulfonation. In certain aspects, said (A), (B), and (D) blocks containno significant levels of olefinic unsaturation, and wherein each (A)block has an average molecular weight of between 1000 and 60,000 andeach (B) block has an average molecular weight of between 2,000 and300,000. In particular embodiments, each (A) block comprises one or morepolymerized segments selected from the group consisting ofpara-substituted styrene monomers, ethylene, alpha-olefins of 3 to 18carbon atoms, 1,3-cyclodiene monomers, monomers of conjugated dieneshaving a vinyl content of less than 35 mol % prior to hydrogenation,acrylic esters, methacrylic esters, and mixtures thereof. In certainaspects, said 1,3-cyclodiene or conjugated dienes are subsequentlyhydrogenated. In certain embodiments, each said (B) block comprises atleast one segment of vinyl aromatic monomers selected from the groupconsisting of polymerized unsubstituted styrene monomers, polymerizedortho-substituted styrene monomers, polymerized meta-substituted styrenemonomers, polymerized alpha-methylstyrene, polymerized1,1-diphenylethylene, polymerized 1,2-diphenylethylene and mixturesthereof. In particular embodiments, each said (D) block comprises atleast one polymer having a glass transition temperature of less than 20°C. and an average molecular weight of between 1000 and 50,000. Inparticular aspects, each said (D) block is selected from the groupconsisting of a polymerized or copolymerized conjugated diene; apolymerized acrylate monomer; a silicone polymer; polymerizedisobutylene and mixtures thereof. In certain embodiments, saidconjugated diene comprises isoprene or 1,3-butadiene having a vinylcontent prior to hydrogenation of between 20 and 80 mol percent. Inparticular embodiments, said (B) blocks are sulfonated to the extent of10 to 100 mol % based on the units of vinyl aromatic monomer present. Inparticular aspects, the vinyl aromatic monomers are present between 10mol % and 100 mol % and are selected from the group consisting ofunsubstituted styrene monomers, ortho-substituted styrene monomers,meta-substituted styrene monomers, alpha-methylstyrene,1,1-diphenylethylene, and 1,2-diphenylethylene. In certain aspects, eachsaid (A) block comprises polymers of one or more para-substitutedstyrene monomers selected from para methylstyrene, para-ethylstyrene,para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene,para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene,isomers of para-decylstyrene, and isomers of para-dodecylstyrene. Inparticular embodiments, said (A) block comprises para-t-butylstyrene andsaid (B) block comprises unsubstituted styrene. In certain embodiments,said (A) block comprises para-methylstyrene and said (B) block comprisesunsubstituted styrene. In particular aspects, said (D) block comprises1,3-butadiene prior to hydrogenation, and wherein 20 to 80 mol % of thecondensed butadiene units in the block have 1,2-configuration prior tohydrogenation.

Additional aspects provide an article of manufacture made with the abovesummarized polymeric materials, wherein said article is selected fromthe group consisting of a membrane, a medical device, a pharmaceuticalcomposition, a moisture transfer membrane, a fluid-absorbing material, afuel cell, a capacitor, a wound dressing, a fabric, a building material,a desalination membrane or device, a membrane for heating, a membrane ordevice for ventilating and air conditioning (HVAC), a packing material,a surface coating, a shunt, a stent, tubing, clothing, bedding, surfacecoatings, fluid absorbing materials, adhesives, fluid collection orstorage bags, sensors, gauges, fluid filters, and the like.

Further aspects provide a method of making the above summarizedpolymeric materials, wherein said method comprises the steps ofcombining at least one sulfonated polymer in solution with at least onenon-sulfonated polymer, allowing the solution to thoroughly mix, andisolating and/or processing the polymer blend. In certain embodiments,said step of isolating and/or processing the polymer blend comprises atleast one of spray drying, precipitation, solvent evaporation,extruding, electrospraying, electrospinning, and precipitating thepolymer blend. In particular embodiments, the method further comprisesthe step of converting the polymer blend to salt form.

Yet additional aspects provide a method of making an article ofmanufacture comprising the above summarized polymeric materials,comprising the steps of combining at least one sulfonated polymer insolution with at least one non-sulfonated polymer, allowing the solutionto thoroughly mix, isolating the polymer blend, and manipulating thepolymer blend to form the article. In certain embodiments, said step ofmanipulating the polymer blend comprises thermal lamination, transfermolding, press molding, extruding, thermal fiber-spinning,electrospinning, electrospraying, painting, dipping, pressure spraying,and the like.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

FIG. 1 shows Doxycycline release from sulfonated polymeric blendedmaterials.

FIG. 2 shows platelet aggregation for CarboSil/SSIBS polymeric blendedmaterials.

FIG. 3 shows platelet aggregation for SB3T-024/SIBS (50:50) sodium saltform polymeric blended materials.

FIG. 4 shows platelet aggregation for SB3T-024/SIBS (50:50) acid formfor polymeric blended materials.

FIG. 5 shows capillary rheometry results presented as a graph depictingthe shear sweep of TecoFlex EG80A/SSIBS Blend (70:30), as described inworking Example 7 herein.

FIG. 6 shows capillary rheometry results presented as a graph depictingthe shear sweep of TecoFlex EG80A/SSIBS Blend (50:50), as described inworking Example 7 herein.

DETAILED DESCRIPTION OF THE INVENTION

Particular aspects are directed to sulfonated polymers and sulfonatedpolymer blended materials, as well as methods for preparing the same. Itwas surprisingly found that uniform, efficacious sulfonation with sulfurtrioxide was possible using the disclosed methods and polymers, whichwould otherwise degrade by hydrolysis (e.g., by acid, catalyzed cleavageof hydrolytically unstable bonds such as with acetyl-sulfate). Theseprocesses are disclosed in PCT application PCT/US2008/063243, which ishereby incorporated herein by reference in, its entirety. As discussedin the PCT application, the sulfonation processes described may beutilized for sulfonating small polymers or large polymers, such asmultiphase copolymers, containing alkene or arene moieties.

In certain embodiments disclosed therein, the method or process forsulfonating polymers has the ability to control the level of sulfonationand thereby control the desired properties. The methods disclosed hereinentail sulfonating a polymer, such as a solid polymerized styrene, in asolvent that does not chemically react in the sulfonation process, andoptionally using a coordination complex of sulfur trioxide and whereinat least one electron pair donor molecule is optionally present in thereaction solution. In certain embodiments, at least one molecule, acoordination complex of sulfur trioxide and at least one electron pairdonor molecule is dissolved in one or more non-reactive solvent(s). Incertain other embodiments, all of the reaction components are dissolvedin one or more non-reactive solvent(s). In certain embodiments, the oneor more non-reactive solvent(s) may form a coordination complex with thesulfur trioxide. In the particular embodiments wherein the non-reactivesolvent forms a coordination complex with the sulfur trioxide,additional electron pair donor molecules may optionally be present inthe reaction solution.

As described herein at other sections, the sulfonated polymer membranesproduced by sulfonation according to the described process havedemonstrated improved properties over sulfonated polymer membranesproduced by other methods, including but not limited to hydrophilicity,inhibition of certain neutrophil-derived proteases, binding and releaseof cationic species (i.e. for ion exchange), and moisture transfer andionic conductivity.

Since increasing hydrophilicity may result in decreasing dimensionalstability or other mechanical properties, polymeric blends allow formodification so as to result in a highly improved product. For example,blending sulfonated polymeric materials with thermoplastic orthermosetting materials can improve thermal stability. Further,sulfonated polymers (in acid form) cannot generally undergo thermalprocessing without significant degradation due to oxidation of thepolymer. While converting the polymer to the alkali salt form allows forsubsequent sintering, it still has limited utility.

As described herein, we have shown in particular aspects that solutionblending of the acid form of the sulfonated polymer with anon-sulfonated polymer, followed by isolation of the polymer blend byeither film casting or precipitation results in a blended material thatcan be thermally laminated. In addition, if the non-sulfonated polymeris a material that may be extruded (such as polyurethane), then thepolymeric blend can also typically be extruded.

In certain embodiments, the process of making the polymer blendsincludes combining at least one sulfonated polymer in solution with atleast one non-sulfonated polymer, followed by isolation of the polymerblend. The blend may then be further manipulated, such as by thermallamination, extrusion, transfer molding, injection molding, and fiberspinning (drawing). The sulfonated blend material may also be convertedto salt form (for example by exposure to saline) and subsequentlyfurther manipulated, such as by melt-processing (including transfermolding, press molding, extrusion, etc.).

Polymers

As disclosed herein, specific embodiments of the sulfonation method orprocess that can be utilized with the polymeric blend materials comprisesulfonating polymers with sulfur trioxide however any suitablesulfonation process known in the art may be employed. The polymers thatare utilized with the polymeric blends are preferably synthetic polymersbut may also include other polymers such as macromolecules, as well asbiological polymers including but not limited to nucleic acids(nucleotides), amino acids, peptides, polypeptides, proteins,glycoproteins, oligomers and/or polymers and/or copolymers containingeither alkene and/or arena and/or hydroxyl moieties. A macromolecule, asused herein, generally refers to a molecule of high relative molecularmass, the structure of which typically comprises multiple repetition ofsegments derived from other molecules, such as for certain oligomers,polymers, or co-polymers. A biopolymer, as used herein, generally refersto a polymer that, at least in part, can be produced by or found inliving organisms, and includes, for example, sugars (monosaccharides,disaccharides, polysaccharides, starches, and the like); amino acids;nucleotides (including oligomers); peptides; polypeptides; proteins;DNA; RNA; proteoglycans; glycoproteins, and any combination thereof. Inaddition, a biopolymer may comprise a combination of a naturallyoccurring polymer and a synthetic polymer. Some examples of combinationsof biopolymers and synthetic polymers include peptidomimetics,non-natural amino acids or peptides, polypeptides and proteinscontaining non-natural amino acids, and others. See, for example, WO003/020735, and Strott, Endocrine Reviews; 23(5):703-732; 2002.

The polymers utilized in the methods or processes of the invention maybe naturally occurring, artificial, or any combination thereof. Thepolymers disclosed may be isolated or in a mixture or solution and/ormay be chemically synthesized. The polymers may be modified (such as byreducing or dehydrogenating) prior to or subsequent to sulfonating.

As described inter alia, the polymers utilized in the processesdisclosed herein may include, but are not limited to, biopolymers,oligomers and/or polymers, such as multiphase large molecular chainpolymers and/or copolymers. Particular embodiments include, but are notlimited to, (a) oligomers and/or polymers and/or copolymers comprisingan ion-containing polymer, (b) biopolymers, or (c) block copolymers.

In certain embodiments, molecules utilized in the methods or processesof the invention comprise an ion-containing oligomeric segment orco-oligomeric segment (ionomer). Typically, ionomers utilized in thepresent invention relate to polyelectrolyte polymers or copolymers thatcontain both nonionic repeat units and at least a small amount of ioncontaining repeating units.

Polymers of various degrees of polymerization are also included in thepresent invention. As one of skill in the art would readily appreciate,the degree of polymerization generally refers to the number of repeatunits or segments in an average polymer chain at a particular time in apolymerization reaction, where length is measured by monomer segments orunits. Preferably, lengths include, but are not limited to,approximately 500 monomer units, 1,000 monomer units, 5,000 monomerunits, 10,000 monomer units, 25,000 monomer units, 50,000 monomer units,100,000 monomer units, 200,000 monomer units, 300,000 monomer units,500,000 monomer units, 700,000 monomer units, or greater or any valuethere between.

The degree of polymerization may also be a measure of the polymer'smolecular weight. Thus, the degree of polymerization is equal to thetotal molecular weight of the polymer divided by the total molecularweight of the repeating unit or segment. Polymers with different totalmolecular weights but identical composition may exhibit differentphysical properties. Generally, the greater the degree of polymerizationcorrelates with the greater melting temperature and greater mechanicalstrength.

In certain embodiments, the oligomer and/or polymer and/or co-polymercomprise a multiphase large molecular chain molecule. In someembodiments the multiphase large molecular chain oligomers and/orpolymers and/or copolymers comprise one or more arene-containing linearside chains, non-arene-containing linear side chains, saturated linearside chains, unsaturated linear side chains, or flexible hydrocarbonlinear side chains.

For purposes of this invention, an “alkene moiety” refers to ahydrocarbon chain containing at least one carbon-carbon double bond. An“arene moiety” refers to a monovalent or divalent aryl or heteroarylgroup. An aryl group refers to hydrocarbon ring system comprisinghydrogen, 6 to 18 carbon atoms and at least one aromatic ring. Forpurposes of this invention, the aryl group may be a monocyclic,bicyclic, tricyclic or tetracyclic ring system, which may included fusedor bridged ring systems. Aryl groups include, but are not limited to,aryl groups derived from aceanthrylene, acenaphthylene,acephenanthrylene, anthracene, azulene, benzene, chrysene, fluoranthene,fluorene, as-indacene, s-indacene, indane, indene, naphthalene,phenalene, phenanthrene, pyrene, and triphenylene. Preferably, an arylgroup is derived from benzene. A heteroaryl group refers to a 5- to14-membered ring system comprising hydrogen atoms, one to thirteencarbon atoms, one to six heteroatoms selected from the group consistingof nitrogen, oxygen and sulfur, and at least one aromatic ring. Forpurposes of this invention, the heteroaryl group may be a monocyclic,bicyclic, tricyclic or tetracyclic ring system, which may include fusedor bridged ring systems; and the nitrogen, carbon or sulfur atoms in theheteroaryl radical may be optionally oxidized; the nitrogen atom may beoptionally quaternized. Examples include, but are not limited to,azepinyl, acridinyl, benzimidazolyl, benzindolyl, 1,3-benzodioxolyl,benzofuranyl, benzooxazolyl, benzothiazolyl, benzothiadiazolyl,benzo[b][1,4]dioxepinyl, benzo[b][1,4]oxazinyl, 1,4-benzodioxanyl,benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl,benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl, benzothienyl(benzothiophenyl), benzothieno[3,2-d]pyrimidinyl, benzotriazolyl,benzo[4,6]imidazo[1,2-a]pyridinyl, carbazolyl, cinnolinyl,cyclopenta[d]pyrimidinyl,6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidinyl,5,6-dihydrobenzo[h]quinazolinyl, 5,6-dihydrobenzo[h]cinnolinyl,6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-c]pyridazinyl, dibenzofuranyl,dibenzothiophenyl, furanyl, furanonyl, furo[3,2-c]pyridinyl,5,6,7,8,9,10-hexahydrocycloocta[d]pyrimidinyl,5,6,7,8,9,10-hexahydrocycloocta[d]pyridazinyl,5,6,7,8,9,10-hexahydrocycloocta[d]pyridinyl, isothiazolyl, imidazolyl,indazolyl, indolyl, indazoly, isoindolyl, indolinyl, isoindolinyl,isoquinolyl, indolizinyl, isoxazolyl,5,8-methano-5,6,7,8-tetrahydroquinazolinyl, naphthyl, naphthyridinyl,1,6-naphthyridinonyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl,5,6,6a,7,8,9,10,10a-octahydrobenzo[h]quinazolinyl, 1-phenyl-1H-pyrrolyl,phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl,purinyl, pyrrolyl, pyrazolyl, pyrazolo[3,4-d]pyrimidinyl, pyridinyl,pyrido[3,2-d]pyrimidinyl, pyrido[3,4-d]pyrimidinyl, pyrazinyl,pyrimidinyl, pyridazinyl, pyrrolyl, quinazolinyl, quinoxalinyl,quinolinyl, quinuclidinyl, isoquinolinyl, tetrahydroquinolinyl,5,6,7,8-tetrahydroquinazolinyl,5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidinyl,6,7,8,9-tetrahydro-5H-cyclohepta[4,5]thieno[2,3-d]pyrimidinyl,5,6,7,8-tetrahydropyrido[4,5-c]pyridazinyl, thiazolyl, thiadiazolyl,triazolyl, tetrazolyl, triazinyl, thieno[2,3-d]pyrimidinyl,thieno[3,2-d]pyrimidinyl, thieno[2,3-c]pridinyl, and thiophenyl (i.e.,thienyl).

For purposes of this invention, an “arene-containing linear side chain”refers to an unbranched hydrocarbon chain consisting only of hydrogen orcarbon, wherein at least one carbon in the chain is replaced with anaryl or heteroaryl group, as defined above.

For purposes of this invention, a “non-arene-containing linear sidechain” refers to an unbranched hydrocarbon chain consisting only ofhydrogen or carbon and containing no aryl or heteroaryl groups withinthe chain.

For purposes of this invention, a “saturated linear side chain” refersto an unbranched hydrocarbon chain consisting only of hydrogen or carboncomprising at least one carbon-carbon double bond or at least onecarbon-carbon triple bond. An “unsaturated linear side chain,” as usedherein, generally refers to an unbranched hydrocarbon chain consistingonly of hydrogen or carbon containing no carbon-carbon double bonds andno carbon-carbon triple bonds.

For purposes of this invention, a “flexible hydrocarbon linear sidechain” refers to a flexible connecting component as taught by U.S. Pat.Nos. 5,468,574 and 5,679,482, of which the disclosures of both arehereby incorporated herein by reference in their entireties.

For purposes of this invention, a “hydroxyl moiety” may refer to anoxygen atom and a hydrogen atom connected by a covalent bond.

The sulfonation process disclosed herein is particularly beneficial tosulfonating multiphase large molecules. The weight of the moleculesutilized in the disclosed methods or processes are preferably at leastapproximately 10,000 Daltons, 15,000 Daltons, 20,000 Daltons, 25,000Daltons, 30,000 Daltons, 40,000 Daltons, 50,000 Daltons, 60,000 Daltons,70,000 Daltons, 80,000 Daltons, 90,000 Daltons, 1 KiloDalton, 2KiloDaltons, 3 KiloDaltons, 4 KiloDaltons, 5 KiloDaltons, or greater orany value there between. Preferably, the size of the molecules is atleast approximately 20,000 Daltons, 50,000 Daltons, 75,000 Daltons, 1KiloDalton, 2 KiloDaltons, or any value there between.

In other embodiments, the measurement of molecular weight may beimportant. The average range of molecular weight (Mw) of the moleculesdisclosed herein includes from about 20,000 grams/mole to about1,000,000 grams/mole, and preferably from about 50,000 grams/mole to900,000 grams/mole.

in general, ionomers utilized in the methods or processes of theinvention contain both polar and non-polar moieties. The nonpolarmoieties of an ionomer are grouped together, while the polar ionicmoieties tend to cluster together and separate from the nonpolar polymerbackbone moieties. This ionic moiety clustering allows forthermoplasticity of the ionomers. Generally, when ionomers are heated,the ionic moieties will lose their attraction for each other and themoieties will freely move, thus allowing for thermoplastic elastomericqualities of the ionic polymer or copolymer.

The processes disclosed herein result in polymers that can be utilizedin the disclosed polymeric blends that have improved properties over theindividual polymers alone. This is due, in part, to little to nocrosslinking, or anhydride formation, with the sulfonated ionomericpolymers, even when the polymers contain unsaturated moieties. Withoutbeing bound by any particular theory, the sulfonation process disclosedherein may react with the unsaturated moiety, resulting in sulfonationat one or more terminal portion of the polymer.

Various types of copolymers, including block copolymers, exist that maybe used with the methods or processes of the invention. For example,alternating copolymers comprise regular alternating A and B chemical orconstitutional units; periodic copolymers contain A and B units arrangedin a repeating sequence (e.g. (A-B-A-B-B-A-A-A-B-B)_(n)); randomcopolymers comprise random sequences of monomer A and B units;statistical copolymers comprise an ordering of distinct monomers withinthe polymer sequence that obeys statistical rules; block copolymers thatare comprised of two or more homopolymer subunits linked by covalentbonds and that may be diblock, tri-block, tetra-block or multi-blockcopolymers. (IUPAC, Pure Appl. Chem., 68: 2287-2311 (1996)).

Additionally, any of the copolymers described may be linear (comprisinga single main chain), or branched (comprising a single main chain withone or more polymeric side chains). Branched copolymers that have sidechains that are structurally distinct from the main chain are known asgraft copolymers. Individual chains of a graft copolymer may behomopolymers or copolymers, and different copolymer sequencing issufficient to define a structural difference. For example, an A-Bdiblock copolymer with A-B alternating copolymer side chains isconsidered a graft copolymer. Other types of branched copolymers includestar, brush and comb copolymers. Any one of these copolymers, or anymixture thereof, may be utilized with certain aspects of the disclosedprocess.

In certain embodiments disclosed herein, the molecule utilized in themethods or processes of the invention comprises a polymer comprised ofat least one block. In certain embodiments, the molecule is athermoplastic block copolymer. In other embodiments, the molecule is ablock copolymer that comprises differentiable monomeric units.Preferably, at least one of the monomeric units of the block copolymercomprises an arene moiety-containing unit. In other preferredembodiments, at least one block comprises a non-arene moiety-containingunit. In certain embodiments, the block copolymer comprises at least twomonomeric units arranged in statistically random order. In otherembodiments, the block copolymer comprises at least two monomeric unitsarranged in ordered sequence. In certain embodiments, the moleculeutilized in the processes disclosed herein includes not only polymers orblock copolymers, but also copolymers with other ethylenicallyunsaturated monomers (such as acrylonitrile, butadiene, methylmethacrylate, etc.).

In certain embodiments disclosed herein, a block copolymer refers to ablock copolymer having at least a first block of one or more monoalkene-arene moiety, such as styrene, ring-substituted styrene,α-substituted styrene, and any combination thereof; and a second blockof a controlled distribution copolymer of a diene moiety and a monoalkene-arene moiety. The block copolymer can be any configuration of “A”and “B” blocks, and such block copolymers can be generated by methodsknown in the art.

For purposes of this invention, a “mono alkene-arene moiety” refers toone or more alkene moieties, as defined above, covalently bonded to anarene moiety, as defined above. An example of a “mono alkene-arenemoiety” is styrene. A “poly alkene-arene moiety” refers to a two or moremono alkene-arene moieties, as defined above, covalently bonded to eachother to form a chain comprising two or more mono alkene-arene moieties.An example of a “poly alkene-arene moiety” is polystyrene. A “dienemoiety” refers to a hydrocarbon chain containing two carbon-carbondouble bonds. In certain embodiments, the diene moiety may beconjugated, unconjugated, or cumulated.

Some specific examples of block copolymers include those described inU.S. Pat. Nos. 4,248,821; 5,239,010; 6,699,941; 7,186,779; 7,169,850;7,169,848;7,067,589; 7,001,950 and 6,699,941 and U.S. Patent ApplicationPublication Nos. 20070021569; 20050154144; 20070004830; 20070020473;20070026251; 20070037927; and 20070055015, all of which are incorporatedherein by reference in their entireties.

In certain embodiments, the polymer comprises a statistical copolymer. Astatistical copolymer is used herein consistent with the commonlyunderstood usage in the art (see, for example, G. Odian, Principles ofPolymerization, 1991). Statistical copolymers are derived from thesimultaneous polymerization of two monomers and have a distribution ofthe two monomeric units along the copolymer chain, which followsBernoullian (zero-order Markov), or first or second order Markovstatistics. The polymerization may be initiated by free radical,anionic, cationic or coordinatively unsaturated (e.g., Ziegler-Natta(metallocene) catalysts), reactive polymerization, ring openingpolymerization or condensation polymerization. According to Ring et al.,(Pure Appl. Chem., 57, 1427, 1985), statistical copolymers are theresult of elementary processes leading to the formation of a statisticalsequence of monomeric units that do not necessarily proceed with equalprobability.

These processes can lead to various types of sequence distributionscomprising those in which the arrangement of monomeric units tendstoward alternation, tends toward clustering of like units, or exhibitsno ordering tendency at all. Bernoullian statistics are essentially thestatistics of coin tossing; copolymers formed via Bernoullian processeshave the two monomers distributed randomly and are referred to as randompolymers. For example, it is possible in a free radical copolymerizationfor the active end, in the case of one embodiment, a styryl orbutadienyl radical, to have essentially no selectivity for styrene vs.butadiene. If so, the statistics will be Bernoullian, and the copolymerobtained will be random. More often than not, there will be a tendencyfor the propagating chain end to have some selectivity for one monomeror the other. In some cases block copolymers can be derived from thesimultaneous copolymerization of two monomers when the preference of thepropagating chain ends for adding the opposite monomers is very low. Theresulting polymer would be categorized as a block copolymer in certainaspects of the present invention.

Statistical copolymers generally display a single glass transitiontemperature. Block and graft copolymers typically display multiple glasstransitions, due to the presence of multiple phases. Statisticalcopolymers are, therefore, distinguishable from block and graftcopolymers on this basis. The single glass transition temperaturereflects homogeneity at the molecular level. An additional consequenceof this homogeneity is that statistical copolymers, such as those ofstyrene and butadiene, when viewed by electron microscopy, display asingle phase morphology with no microphase separation. By contrast,block and graft copolymers of styrene/butadiene, for example, arecharacterized by two glass transition temperatures and separation intostyrene-rich domains and butadiene-rich domains. It should be noted thatmembranes of the invention which are produced from statisticalcopolymers originally having a single glass transition temperature and asingle phase morphology do not necessarily exhibit a single phasemorphology or a single glass transition temperature after sulfonationbecause of chemical changes in the polymer effected by the sulfonation,in combination with the physical changes effected by the castingprocesses of the invention.

Pseudo-random copolymers are a subclass of statistical copolymers whichresult from a weighted change in the monomer incorporation that skewsthe distribution from a random arrangement (i.e., Bernoullian) isdefined as statistical. Linear arrangements have been described here,but branched or grafted including star arrangements of monomers arepossible as well. In addition, block copolymers of styrene andhydrogenated butadiene, isoprene, or equivalent olefin can be employed.The block architecture can be monomeric units comprising diblock,triblock, graft-block, multi-arm starblock, multiblock, segmented,tapered block, or any combination thereof.

One particular advantage provided by certain embodiments includes theability to apply the disclosed process to non-styrenic high molecularweight polymers. Thus, in certain embodiments disclosed herein, thepolymers utilized in the processes disclosed do not comprise a monoalkene-arene moiety or segment, such as a styrene segment. In certainother embodiments disclosed herein, polymers utilized in the processesdisclosed do not contain poly alkene-arene moieties or segments, such aspolystyrene. In certain such embodiments, the polymer includes moietiesor segments comprising unsaturated carbon-carbon double bonds, which areable to be sulfonated. Some examples of such polymers include, but arenot limited to polybutadiene or polyisoprene. With certain polymers thatare highly reactive in a particular solution, the reaction conditionsmay be further altered by, e.g. lowering the reaction temperature and/orfurther cleaning the sulfonated polymer in order to remove residualsolvent and/or undesirable by-products or contaminants (?).

In particular, certain embodiments disclosed herein relate to thesulfonation of polymers comprising one or more of the followingmoieties: alkane, alkene, alkyne, and arene, each of which may beoptionally substituted by one or more of the following functionalgroups: carboxylic acid, urea, ester, urethane (carbamate), alkene,amide, benzene, pyridine, indole, carbonate, thioester,arcylate/acrylic, ether, amidine, ethyl, acid versions of aliphaticcompounds that contain alkenes, alkanes or alkynes, imidazole, oxazole,and other possible combinations of heteroatom containing groupssusceptible to loss of water and/or disassembly. Each of the termslisted above has its standard definition known to one skilled in theart.

Some specific examples of polymers or polymer moieties or segments thatmay be utilized by the processes disclosed herein include but are notlimited to polyethylene (PE), polypropylene (PP), polyethylene oxide(PEO), polystyrene (PS), polyesters, polycarbonate (PC), polyvinylchloride (PVC), polyamides, halogenated polymers or copolymers such asperfluorinated copolymers, poly(methyl methacrylate) (PMMA),acrylonitrile butadiene styrene (ABS), polyamide (PA),polytetrafluoroethylene (PTFE), polylactic acid (PLA), polyvinylidenechloride (PVDC), styrene-butadiene rubber (SBR),styrene-ethylene/butylenes-styrene (SEBS);styrene-ethylene/propylene-styrene (SEPS), ethylene-styrene interpolymer(ESI), styrene acrylate, polyetherether ketone (PEEK), polyethyleneterephthalate (PET or PETE), and any combination of these or others.

Solvents

The solvent(s) used in the sulfonation reaction are preferably anysolvent that does not react during the sulfonation process, is easilyhandled in commercialization, processes, and offers the appropriatesolubility characteristics for the polymer undergoing sulfonation and/orthe final sulfonated polymer. In certain embodiments, the solvent ispreferably anhydrous.

In certain instances, the non-reacting or inert solvent comprises ahydrocarbon, preferably a halogenated hydrocarbon, such as a chlorinatedhydrocarbon solvent. Some examples include, but are not limited toethylene dichloride, perchloroethylene, trichloroethylene,1,1,1-trichloroethane (1,1,1-TCA), dichloroethane (including1,1-dichloroethane (1,1-DCA), and 1,2-dichloroethane (1,1-DCE)), carbontetrachloride, vinyl chloride (VC), tetrachloroethane, chloroform(trichloromethane), dichloethane, methylene dichloride (MDC),tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide(DMAC), or any combination of these. In addition to chlorinatedhydrocarbon solvents, other non-reacting solvent(s) include but are notlimited to carbon disulfide, nitro compounds, and super-critical carbondioxide (which behaves as a supercritical fluid, under certainconditions, and any combination of these or other non-reacting solvents.

Certain embodiments of the process disclosed herein allow for a range ofthe amount of solvent(s) used in the sulfonation reaction. For example,in certain embodiments, the solvent ranges from 30-99.9% of the reactionsolution. In other embodiments, the solvent ranges from 50-99.5% of thereaction solution. In still other embodiments, the solvent ranges fromless than approximately 10%, 8%, 5%, 4%, 3%, 2%, or 1% by weight of thepolymer solution. In other particular embodiments, the solvent rangesfrom less than approximately 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% by weightof the sulfur trioxide.

While the disclosed process allows for a range of molar concentrationsor percent solids, one of the limiting factors is the ease of handlingthe reaction mixture. For example, if the solution becomes too viscous(for example, when the solids concentration is too high), homogenousdispersion of the reaction components throughout the solution may beprevented. A solution that is too viscous, presents a potential for(localized) overheating, or non-uniform heating during the reaction.

The solution viscosity of any particular sulfonated molecule (includinga polymer) may be varied over a wide range and will depend on a numberof variables. One of the variables is the molecular weight of, themolecule, other variables include the (polymer) solids concentrationused in the reaction solution, the target/final sulfonation level of thesulfonated molecule product, the solvent(s) of choice, and thetemperature of the reaction mixture. By controlling the moleculesolution viscosity at the outset, the very fast sulfonation kinetics canalleviate many of the aforementioned problems, such as superheating,from occurring. Thus, the proper tailoring of the reaction parametersare important for achieving a uniformly sulfonated molecule product(which provides for improved precision in polymer sulfonation). Propertailoring of the reaction variables at the onset may allow for theapplication of a polymer system that allows for a range of miscibility.Additionally, the proper tuning of the reaction variables in order tomaintain fast reaction kinetics can allow for production of a sulfonatedmolecule that is insoluble in the non-reacting solvent(s).

One advantage provided by several of the embodiments disclosed hereinincludes the ability to reuse or recycle the solvent(s) that are duringthe course of the sulfonation reaction. Because sulfonation with acetylsulfate presents a heterogeneous reaction mixture that includes organic,mineral and organic acid, as well as aqueous components, re-capture ofpure solvent following the sulfonation reaction is cumbersome andprohibitively expensive. Thus, in order to reuse the solvent(s) of theprocesses described herein following moderated sulfonation using thesulfur trioxide reagent as described, the solvents are captured as thesulfonated molecule product is dried, immediately following sulfonation.As the solvent(s) can be easily reused for other sulfonation reactionssolvent and disposal costs can be reduced as the only waste isassociated with the a small amount lost during the sulfonated moleculedrying step.

For example, mixing the complete output of the sulfonation reaction(where the polymer or other molecule may or may not be in solution) withone or more non-solvent(s) of the polymer or other molecule may capturethe solvent. Following precipitation of the molecule, the solvents maybe collected by filtration or other methods. Generally, non-polaraliphatic hydrocarbons, which lack ionizable hydrogen atoms, arewell-suited non-solvents. Some examples include, but are not limited toalkanes, such as heptane, and hexane, or cyclic alkanes, includingcyclopentane, cyclohexane, cycloheptane, and cyclooctane, which arerelatively non-polar. Other suitable non-solvents can be readilyascertained by one of skill in the art without undue experimentation.

The solvent(s) are then removed from the sulfonated molecule reactionmixture, such as by decanting or filtering. In certain embodiments thatuse non-miscible solvents that may have similar boiling points, such asdichloromethane or pentane, the solvent may be separated by fractionaldistillation. The sulfonated molecule is then allowed to dry, whether byambient air, drying oven, or desiccation. The final sulfonated moleculetypically produces a dry powder or flake product.

Electron Pair Donor Agent

Sulfur trioxide (SO₃) is a highly reactive electron acceptor or Lewisacid, and readily interacts with electron pair donors or Lewis bases to,form coordination compounds, also referred to as “coordination adducts”or “coordination complexes” herein. Formation of a coordination complexwith sulfur trioxide provides a method of regulating its reactivity,particularly in some of the embodiments of the sulfonation reactionsdescribed herein.

Without being bound by any particular theory, certain embodiments of thepresently disclosed process benefit from the addition of an electronpair donor agent or blocking agent to the sulfonation reaction. Onepossible theory as to how the addition of an electron pair donor agentor blocking agent renders the sulfonation reaction more efficient isbased on the attraction of the agent to the sulfur trioxide. Thischemical interference may assist to regulate the sulfonation reaction asthe sulfur trioxide reacts with the styrene or general aromatic rind ofthe polymer or other molecule. In particular aspects, the addition of anelectron pair donor agent or blocking agent produced the surprisingresult of enhancing the sulfonation process for large molecular weightor long chain molecules utilizing sulfur trioxide in the polymericsulfonation reaction.

Typically, the electron pair donor agent utilized in the syntheticsulfonation scheme employing sulfur trioxide in the methods of processdisclosed herein includes, but is not limited to, a bidentate electronpair donor agent which is soluble in a non-reactive organic solvent. Inparticular embodiments, the electron pair donor agent comprises anorganic species comprising at least two hetero atoms separated by atleast two other atoms (for example, representing a 1,4-arrangement ofheteroatoms; a 1-5-arrangement of heteroatoms, or a 1-6-arrangement ofheteroatoms, etc.). Some examples of electron pair donor agents that maybe used with the present process include, but are not limited to cyclicor non-cyclic carboxylic acid esters, amines (including tertiaryamines), sulfides, sulfoxides, carboxylic acids, thiols, amides, ethers,thioethers, and sulfonamides. In certain embodiments, at least oneelectron pair donor agent comprises trimethylamine, triethylamine,pyridine. N,N′-diethylaniline, 2-methlypyridine, 2,6-dimethylpyridine,N-ethylmorpholine, 1,2-dimethoxyethane, 1,3-dimethoxypropane,1,4-dioxane, or others.

Additives

Compatible polymer blends can often be produced or enhanced by additionof monomeric or polymeric materials without any chemical reaction. Avariety of additives have been utilized in polymeric blends, includingthe monomeric additives of solvents, plasticizers, surfactants, fibers,and fillers; and the polymeric additives including but not limited toblock copolymers or graft copolymers. Additionally, impact modifiers maybe added, such as acrylics. Finally, the sulfonic acid component of theblend may be neutralized or on exchanged to incorporate ammonia orammonium such as NH₄+, benzyl trimethyl ammonium or catalytic metal ions(oxovanadium ion, cobalt ion, rhodium ion, etc.).

Reaction Conditions

A feature of the methods or processes the invention includes thesurprising result of a controllable sulfonation reaction that results ina sulfonated molecule product with low levels, or the absence of,undesirable side-products or degradation. In contrast, even when verylow temperatures are utilized for sulfonation reactions usinguncomplexed sulfur trioxide, sulfonation leads to a complex mixture ofsulfonated polymer product and a variety of undesirable side reactions.Typically, dehydrogenation and oxidation accompany sulfonation, and theend product contains complex mixtures of hydroxyl and carbonylcompounds, carboxylic acids, and unsaturated compounds, as well as theirderived sulfates, sulfonic acids, sulfones, sultones and sulfonateesters. It is expensive and cumbersome to purify the sulfonated polymerin the presence of these undesirable sulfonation reaction side-products.

Several factors contribute to the efficiency of the sulfonationprocesses disclosed herein, including, but not limited to, thesulfonating agent, the polymer, the molecular weight of the polymer, thesolvent, the concentration of reactants in the sulfonation solution, therate and amount of agitation or mixing, the purity of the solvent andreactants, the temperature of the reaction and reactants, the molarratios of reactants, solvent(s) and optional electron pair donoragent(s), the modes of reactant feeding, the size of the sulfonationvessel, the sequence of addition to the solution of each of thereactants, the aging of the finished reaction mixture, and others.

In some embodiments, the concentration of the polymer utilized in thesulfonation reaction solution is less than approximately 50% solids byweight, less than approximately 40% solids, less than approximately 30%solids, less than approximately 20% solids, less than approximately 10%solids, less than approximately 5% solids, less than approximately 4%solids, less than approximately 3.5% solids, less than approximately 3%solids, less than approximately 2% solids, less than approximately 1%solids, less than approximately 0.5% solids, or less or any value therebetween. In some particular embodiments, the concentration of thepolymer utilized in the sulfonation reaction solution is in the range ofapproximately 2-5% solids. In still other particular embodiments, theconcentration of the polymer utilized in the sulfonation reactionsolution is approximately 3.5% solids.

In certain embodiments disclosed herein, the concentration of at leastone electron pair donor agent is at least approximately 1.0 mol % donorpolymer per mole of sulfur trioxide. In other embodiments, theconcentration of at least one electron pair donor molecule is at leastapproximately 2.0 mol %, 3.0 mol %, 4.0 mol %, 5.0 mol %, 6.0 mol %, 7.0mol %, 8.0 mol %, 9.0 mol %, 10 mol %, 20 mol %, 30 mol %, 40 mol %, 50mol %, 60 mol %, 70 mol %, 80 mol %, 90 mol %, 100 mol %, 110 mol %, 120mol %, 150 mol %, 175 mol %, 200 mol %, 225 mol %, 250 mol %, 275 mol %,300 mol %, 325 mol %, 350 mol or any value there between donor agent permole of sulfur trioxide.

The various polymers that may be utilized in the sulfonation reactiondisclosed herein may be exposed to the sulfonating reagent in the formof a solid, liquid, or gas (including vapor). The molecular species orsulfonating reagents may be completely or partially soluble in thereaction medium such that the reaction medium comprises a solution,mixture, gel, emulsion, colloidal suspension, sol, or the like or anycombination thereof. In some particular embodiments, the polymer isintroduced into the sulfonation reaction in a solid form, including theform of pellets, crumb, chunks, flat sheets, dispersed particles, or thelike. In other embodiments, the polymer is introduced to the sulfonationreaction in liquid form (in solution or in mixture form) with the otherreaction components. Still, in other particular embodiments, themolecule is introduced to the sulfonation reaction in a gaseous or vaporform. In some embodiments, the molecule is introduced into thesulfonation reaction in any combination of these forms.

The degree of sulfonation is defined in the art as the quotient of thetotal number of sulfonic acid groups in the molecule and the totalnumber of self-repeating monomeric units. Adjusting one or more of theseveral factors that contribute to the efficiency of the sulfonationprocess described herein may regulate the degree of sulfonation. Forexample, by increasing or decreasing the temperature beyond thepreferred range, the sulfonation reaction slows and the resultingsulfonated polymer exhibits a low percent by weight of sulfonic acidresidues. Moreover, by increasing or decreasing the speed beyond thepreferred range, the polymer may precipitate out of solution and theresulting sulfonated polymer is not uniformly sulfonated.

As described inter alia, the degree of sulfonation of a particularpolymer disclosed herein may range from approximately 2-100 mole mol %.Preferably, the sulfonated polymers disclosed herein exhibit a degree ofsulfonation of approximately 10 mol %, 20 mol %, 30 mol %, 40 mol %, 50mol %, 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 96 mol %, 97mol %, 98 mol %, 99%, 100 mol %, or any value there between. Mostpreferably, the sulfonated polymers disclosed herein exhibit a degree ofsulfonation of approximately 25 mol % to 80 mol %.

Certain embodiments of the disclosed process are characterized by a lowreaction temperature and short reaction time. Using a low reactiontemperature facilitates production of a highly efficiently sulfonatedproduct polymer that exhibits a desirable and controllable degree ofuniform sulfonation with little to no generation of undesirableside-products. In certain embodiments, the starting temperature of thereactants and/or the temperature of the reaction mixture and/or thetemperature of the sulfonation reaction is approximately −40° C., −30°C., −25° C., −20° C., −15° C., −10° C., −5° C., 0° C., 5° C., 10° C.,15° C., 20° C., 25° C., 30° C., or any value there between. The startingtemperature or reaction temperature or sulfonation temperature may allbe the same or each temperature may be different. For example, thestarting temperature may be approximately −20° C., and increase slightlyas the reaction mixture is mixed or processed due to the increase inkinetic energy. Furthermore, the sulfonation reaction itself may beexothermic, thus increasing the reaction temperature.

The lower limit for the temperature of the reaction mixture during thereaction is chosen such that a relatively uniform solution is stillpresent, i.e. such that no component of the mixture is present as asolid aggregate. While the reaction temperatures ranges may varysomewhat, the sulfonation reaction slows at colder temperatures, whiledegradation of the polymer may occur and/or formation of undesirablereaction side-products (such as crosslinking) occurs at temperaturesthat are too high.

In addition, the sulfonation process can be carried out either undernormal pressure or under increased pressure. Overall pressure ispreferably in the range of approximately 1-200 bar. In certainembodiments, the pressure is approximately 1 bar, 5 bar, 10 bar, 20 bar,50 bar, 75 bar, 100 bar, 120 bar, 150 bar, 180 bar, 200 bar, or anyvalue there between.

Another surprising result of the presently disclosed process relates tousing the thermo-kinetic effect of the high speed mixer wherein theshear rate is from approximately 5 s⁻¹, 10 s⁻¹, 15 s⁻¹, 20 s⁻¹, 30 s⁻¹,40 s⁻¹, 50 s⁻¹, or greater or any value there between that is capable ofincreasing the temperature of the sulfonation reaction in a controlledand uniform manner. It was found that when the temperature of thesulfonation reaction was uniformly increased, the reaction yields a moreuniformly sulfonated polymer. Moreover, when the sulfonation reaction isconducted at very low temperatures (such as −20° C.), the kinetic energyof the high speed mixing or agitating environment aids in thesulfonation reaction.

Sulfonation reactions that take place in a high speed mixing oragitating environment typically prevent the polymer from settling and/orprecipitating out of the solvent. As one of skill in the art wouldrecognize, the speed that is needed to prevent the molecule fromprecipitating out of the solvent may vary depending on the particularequipment (such as a spinning plate thin film reactor, or acounter-rotating shaft thin film reactor) used for the sulfonationreaction. Thus, the high-speed mixer assists in maintaining the reactioncomponents in solution or dynamic mixture and prevents the sulfonatedpolymer from aggregating.

The sulfonation reaction process may further be varied by the sequencein which the reactants are added to the reaction mixture or solution. Incertain embodiments, the sulfonation reaction components may be added inany order or simultaneously. In other embodiments, the polymer isdissolved in or otherwise placed in contact with one or morenon-reactive solvent(s) prior to contact with sulfur trioxide and/or theoptional electron pair donor agent(s). In other particular embodiments,the non-reactive solvent may be first placed in contact with sulfurtrioxide and/or the optional electron pair donor agent(s) prior toadding the polymer. In still other particular embodiments, the polymermay be placed in contact with sulfur trioxide and/or the optionalelectron pair donor agent(s) prior to addition of the non-reactingsolvent. Thus, in certain embodiments, the sulfur trioxide utilized inthe processes disclosed herein is present in the reaction in the form offree sulfur trioxide. In certain other embodiments, the sulfur trioxideutilized in the processes disclosed herein is present in the reaction inthe form of a coordination complex with at least one electron pair donoragent. In some particular embodiments, the non-reacting solvent iscapable of forming a coordination complex with the sulfur trioxide.

Depending on several factors, including the starting polymer and thedegree of sulfonation desired, as well as the overall sulfonationreaction kinetics, the sulfonation reaction can be completed within therange of approximately 5 to 2,000 seconds (or approximately 33 minutes).In certain embodiments, the reaction kinetics allow for the reaction tobe completed within approximately 1 second, 2 seconds, 3 seconds, 4seconds, 5 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds,120 seconds, 140 seconds, 160 seconds, 180 seconds, 200 seconds, 300seconds, 400 seconds, 500 seconds, 600 seconds, 800 seconds, 1000seconds, 1500 seconds, 2000 seconds, or any value there between. Incertain embodiments, the sulfonation reaction takes no more thanapproximately 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, or ahalf-hour. In certain embodiments, the reaction is complete withinapproximately two minutes or less, one minute or less, or 30 seconds orless, or any value there between.

The sulfonation reaction can be terminated by exhausting reactioncomponents, or quenching by the addition of water or other sacrificialreactant (such as ethanol or methanol or amines such as ammonia).Alcohols convert sulfur trioxide to esters of sulfuric acid, thusceasing sulfonation of the polymer. However, it is worth noting thatsuch (sulfonic acid) esters are potent alkylating agents and must behandled with care. In addition, it is possible to terminate the reactionby selecting and adding a solvent capable of separating the sulfonatedpolymer from the reaction system, i.e. precipitation.

Once the sulfonation reaction has been terminated, the sulfonatedpolymer may then be isolated by filtration, precipitation,chromatography, or other purification methods known in the art. Thesulfonated polymer may be washed (if necessary), by standard techniquesknown in the art. For example, the sulfonated polymer may be washed bysubmersion in a washing liquid (including but not limited to deionizedwater or an aqueous salt solution) followed by filtration, or spraywashed on a film evaporator. The use of an aqueous salt solution as ameans of generating the polymeric salt may be preferable, if thesulfonated polymer is not required to be in acid form although it isnecessary to rinse excess salt solution from the polymer prior to itsuse in further processes.

Another method involves the preparation of a blend by combining thesulfonated polymer solution, immediately post sulfonation, with asolution of another polymer (or polymers) to comprise the blend, mixingthe two solutions adequately and isolating the blend by precipitation orsolvent removal by means standard in the industry (such as reducedpressure rotary evaporation or spray drying). An ensuing purificationstep to remove any traces of sulfuric acid for example) alleviates theneed to first isolate and purify the sulfonated polymer, redissolve andcombine with another polymer to form the blend. The aforementioned anddescribed manipulation removes an entire step as described in the latterexample. The polymer may then be dried at room temperature or atelevated temperature and under vacuum (negative or reduced pressure). Inother embodiments, the blended polymeric solution may be cast, sprayed,or isolated as a solid and subsequently subjected to thermoforming(simultaneous cospraying of solutions of sulfonated and non-sulfonatedpolymers, lamination of non-sulfonated polymer film with eithersulfonated polymer film or films comprised of blends of sulfonated andnon-sulfonated polymer film or lamination of blend films with sulfonatedpolymer film.

As disclosed herein inter alia, another beneficial feature of thedisclosed process includes the cost-saving ability to recycle thesulfonation reaction solvent(s) and optional electron pair donoragent(s). As described herein, the electron pair donor agent does notchemically participate in the sulfonation reaction. Thus, it can beeasily removed from the sulfonated polymer at the termination of thesulfonation reaction. In the case of dioxane, residual traces evaporatefrom the precipitated sulfonated polymer during the drying step. Theability to reuse or recycle the solvent(s) and/or electron pair donoragent(s) of the presently disclosed process makes the processesdisclosed herein amenable to use a multitude of polymers in a widevariety of applications.

In addition to batch processing, the presently disclosed methods ofsulfonating polymers may be utilized for large scale sulfonation ofpolymers by utilizing a continuous feed process, i.e. an industrialscale apparatus that moves the polymer to be sulfonated continuouslythrough a sulfonating reaction mixer and into a holding tank oncesulfonated. In this regard, the throughput of the process is increasedby several orders of magnitude. Such a large-scale process increasesyield, lowers cost, and produces more uniform sulfonated polymers, allof which make it readily adaptable for commercialization.

Sulfonated Polymers

Previously used processes for sulfonating polymers, such as polymers,with sulfur trioxide resulted in high levels of cross-linking polymersand high levels of undesirable side-products, (U.S. Pat. Nos. 2,475,886;2,283,236; and 2,533,211, all of which are hereby incorporated byreference in their entirely).

The sulfonated polymers generated by the herein disclosed processesinclude sulfonated and/or polysulfonated oligomers and/or polymersand/or copolymers containing, for example, either alkene and/or areneand/or hydroxyl moieties with little or no residual or contaminatingsulfuric acid remaining following removal of water from the solvent(s).In certain embodiments, the sulfonation reaction is performed under ananhydrous and controlled atmosphere, which may include inert gases suchas argon, nitrogen or the like. Depending on the particular startingmaterial, the resulting sulfonated polymers (such as a sulfonatedionomeric copolymer) may be soluble in water, or insoluble in water butsoluble in alcohol (for example n-propanol or butyl alcohol or anyvariety of binary, ternary or higher solvent mixtures).

Additionally, the sulfonated polymers generated by the processesdisclosed herein will have little, if any, cross-linking polymericcomponents or other undesirable side-products. In embodiments thatutilize an ionomeric copolymer in the sulfonation reaction there will belittle or no resulting cross-linked ionomeric copolymer(s).

Furthermore, the sulfonated polymers generated by the disclosed processare very uniformly sulfonated or polysulfonated. In certain embodiments,the sulfonated polymer is uniformly sulfonated or polysulfonated fromapproximately 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85% 90%, 91%, 92%, 93%,94%, 95%, 96%, 97%, 98%, 99% by weight; or greater or any value therebetween. In certain embodiments, the sulfonated polymer prepared by thedisclosed process is uniformly sulfonated or polysulfonated at 10-90% byweight.

Uniformly sulfonated polymer membranes (such as sulfonated polymermembranes) typically have higher ionic conductivities, higher watertransfer rates, and reduced water absorption at lower sulfonation molepercent conversion levels than non-uniformly sulfonated polymer of thesame chemical structure. Thus, one of skill in the art would inferuniformity of a particular sulfonated polymer based on several polymermechanical and electrochemical properties, as demonstrated for theuniformly sulfonated polymers disclosed herein.

The method of sulfonating arene-containing polymers and the varioussulfonated polymers disclosed herein may be used directly or furthermodified before use. For example, the sulfonated polymers disclosedherein may be used as the free acid or as a salt thereof such as that ofan alkali metal, or other metal salt thereof, including but not limitedto metal ions, preferably mono-, di- and trivalent ions of metals inGroups IA, IB, IIA, IIB, IIIA, IIIB, and VIII of the Periodic Table ofElements. The metal ions may be complexed or uncomplexed, and can beused alone or in any mixture, thereof. Some examples of suitable metalions include: lithium, sodium, potassium, rubidium, silver, mercury,copper, magnesium, calcium, strontium, cadmium, tin, iron, barium,palladium, scandium, yttrium, and cesium salts, or any combinationthereof. Compounds of these metals may be used as hydroxides, chlorides,bromides, fluorides, oxides, alcoholates, hydrides, carboxylates,formates, acetates, alkoxides such as methoxides or ethoxides, nitrates,carbonates, bicarbonates, and the like.

The degree of neutralization with a metal ion-containing base may beachieved by various methods known in the art. In particular, theneutralization reaction may be carried out by adding the metal compound,directly or in solution, to a solution of the sulfonated polymer and,following neutralization, precipitating and separating the resultingpolymer. Another particular method of neutralization may entail meltblending the sulfonated polymer with the metal compound. This reactionis preferably conducted at elevated temperatures in order to facilitatehomogenous distribution of the metal compound and to volatize anyneutralization byproduct that can include water, alcohols, and smallorganic species.

Alternatively, the sulfonated polymer may already be in an allneutralized salt form or in a partially neutralized form and protonation(acidification) is desired. Acidification of the sulfonated polymer maybe carried out under conditions, which allow for a homogenous uniformdistribution of the acid in the sulfonated polymer. The resultingmetal-salt acidification product may then be used directly or treatedfurther in order to remove any metal salt by-product.

The degree of sulfonation and/or neutralization may be measured byseveral techniques that are readily available to the skilled artisan.For example, nuclear magnetic resonance (NMR), titration, or elementalanalysis may be used to determine the overall degree of functionality.Moreover, the sulfonated polymers may be analyzed for sulfonation andother characteristics by using Fourier Transform Infrared spectroscopy(FTIR) or other technique in conjunction with optical spectroscopy,infrared spectroscopy, nuclear magnetic resonance, electron spinresonance and others. In addition, the titration of a solution of ablock copolymer with a strong base may be utilized to determine thedegree of functionality and/or neutralization (metal sulfonate saltcontent). Neutralization is generally based on the percentage ofsulfonate ions as compared to the total sulfonic acid and sulfonategroup functionality. Purity may be assessed by a number of methods thatinclude liquid chromatography, in particular gel permeationchromatography (GPC) and mass spectrometry (matrix assisted laserdesorption ionization—MALDI MS) as well as indirectly by a variety of invitro and in vivo biocompatibility tests that include but are notlimited to in vitro cytotoxicity by MEM or direct contact methods aswell as by implantation of the material and subsequent histopathology ofthe excised tissue from around the implanted material.

Moreover, compositions and articles prepared by the sulfonated polymersdisclosed herein may also contain non-reactive additives, such aschemical additives, fillers, or reinforcements, which do not react withthe sulfonated polymer. Some examples include, but are not limited toplasticizers, lubricants, anti-oxidants, anti-static agents, colorants,flame retardants, fillers, mold release agents, nucleating agents,stabilizers or inhibitors of oxidative, thermal and ultraviolet lightdegradation, and fibrous or other reinforcements (including but notlimited to silica, carbon black, clay, glass fibers, organic fibers,calcium carbonate, and the like).

The sulfonated polymers disclosed herein may be further modified beforeuse by processes, such as cross-linking, that improve their mechanicalproperties. In other embodiments the polymer to be sulfonated may bepreformed or cross-linked, or a combination of the two prior tosulfonation. For example, a cross-linked bead of styrene-divinyl benzenecopolymer may be subjected to sulfonation to yield an ion-exchange beador may be insoluble in the sulfonation solvent medium thus resulting insulfonation of the surface. For example polyethylene terephthalate orparylene may be sulfonated by the sulfonating complex without theaggressive and degradative affects of neat sulfur trioxide.

In certain embodiments disclosed herein, sulfonated polymer have a totalmole percent (mol %) sulfonation of approximately 2-99% or greater. Inspecific embodiments, the mol % of sulfonation is approximately 2%, 5%,10%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 90%, 91%, 92%, 93%,94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or greater or any value therebetween. The mole % of sulfonation may be varied during the process toproduce from 5-99% sulfonation. The sulfonated polymers disclosed hereinexhibit exceptionally good qualities. Depending on the particularstarting material, qualities such as toughness, clarity, formability,oil/grease resistant barrier, draw ability, heat seal, hot tack,abrasion resistance, electrical conductivity, tensile strength,stiffness, hardness, tensile impact, stress crack resistance, adhesion,durability, and melt strength are enhanced by the sulfonation processdisclosed. The sulfonated polymers may be used for sizing agents,protective colloids, adhesives, dispersing agents, thickening agents,tanning agents, packaging resins, conventional extrusion/co-extrusionblown film, cast film, other films, extrusion coating equipment, moldingresins, automotive parts, golf ball resins, packaging seals, moldedgoods (e.g. cosmetics, or sporting goods), and may be used for electrospraying or electro spinning in the form of a fiber, foam, sheet, orencapsulate, or any combination thereof.

In certain embodiments, membranes may be produced utilizing thesulfonated polymers disclosed herein by spray processing, such asthermal spray coating. Thermal spray processing allows for a relativelythin (approximately 0.005″) and thick (approximately 0.250″) coatings ofpolymers onto a variety of materials and is effective to produceprotective barriers. Some examples of polymers that have been used forthermal spraying include but are not limited to polyethylene,poly(methylmethacrylate), poly(ethylene-methylmethacrylate) copolymer,ethylene methacrylic acid copolymer, polyetheretherketone polymer,polyphenylene sulfide liquid crystal polymer, polyamide (nylon),phenolic epoxy, Tefzel, and post consumer commingled polymer.

In general, the polymer powder is injected into a heat source (such as aflame or plasma) and moved to a pre-heated substrate by way of a spraygun or other apparatus. The thickness of the coating depends on thenumber of passes of the spray gun across the substrate.

In still other embodiments, membranes may be produced utilizing thesulfonated polymers disclosed herein by melt extrusion. Generally, meltextrusion involves feeding polymers into a drive extruder as raw plasticmaterial, which transports the material to a die head while it issimultaneously heated, mixed, pressurized and metered. At the die head,the polymer takes up the approximate shape of the article and is thencooled either by water or air to give the final shape. As the polymercools it is drawn along by haul-off devices and either coiled (for softproducts) or cut to length (for hard products).

In addition to the above-mentioned processes, membranes may also beproduced using sulfonated polymers disclosed herein by using arotogravure process or a slot casting process. For a slot castingprocess, the polymer dissolved in a solvent is pressure extruded in auniform thickness and viscosity onto carrier or support creating acontinuous film. Rotogravure is process wherein a cylinder with surfacecavities is coated with a liquid. As the cylinder turns, it transfersthe liquid in the surface cavities to a carrier or support forming acontinuous film. Generally, uniformly sulfonated polymer casts evenlywith little or no signs of macro-phase separation. When membrane castingis even, it produces stronger membranes because the density andcross-sectional thickness are uniform.

The polymeric blend materials may further be electrospun orelectrosprayed directly from solution to form tubes, rods, and otherformed materials. In certain aspects, the polymeric blend materials maybe spun into fibers for vascular grafts or other applications.

Certain embodiments relate to a polymer blend that is insoluble in waterand is composed of a sulfonated aryl-containing copolymer and at leastone material selected from the group consisting of homo-polymer orcopolymers. The homo-polymer or copolymers may comprise polyurethane, asegmented polyurethane, an arylene-vinyl containing block copolymer, apolysiloxane, a polyamide, a polyurethane urea, a polyketone, apolyester, a poly(ether-ester) (such as polydioxanone), a polyanhydride,a poly(ortho ester), a polyacrylate, a polyalkylene, a polycarbonate, apoly(carbonate urethane) a fluoropolymer, a polysulfone, carbohydratepolymers (such as cellulose and starch), a polypeptide, a polyether,and/or a poly(vinylalcohol), poly(ethylene-co-vinyl acetate),poly(ethylene-co-vinyl alcohol). In certain embodiments, the sulfonatedcopolymer comprises a block copolymer with at least two polymer endblocks (A) and at least one polymer interior block (B) wherein: a. each(A) block is a polymer block resistant to sulfonation and each (B) blockis a polymer block susceptible to sulfonation, said (A) and (B) blockscontaining no significant levels of olefinic unsaturation; b. each (A)block independently having a number average molecular weight between1,000 and 60,000 and each (B) block independently having a numberaverage molecular weight between 2,000 and 300,000; c. each (A) blockcomprising one or more segments selected from polymerized (i)para-substituted styrene monomers, (ii) ethylene, (iii) alpha olefins of3 to 18 carbon atoms; (iv) 1,3-cyclodiene monomers, (v) monomers ofconjugated dienes having a vinyl content less than 35 mol percent priorto hydrogenation, (vi) acrylic esters, (vii) methacrylic esters, and(viii) mixtures thereof, wherein any segments containing polymerized1,3-cyclodiene or polymerized conjugated dienes are subsequentlyhydrogenated and wherein any (A) block comprising polymerized ethyleneor hydrogenated polymers of a conjugated, acyclic diene have a meltingpoint greater than 50° C.; d. each (B) block comprising segments of oneor more vinyl aromatic monomers selected from polymerized (i)unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers,(iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v)1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixturesthereof; e. said (B) blocks are sulfonated to the extent of 10 to 100mol percent, based on the units of vinyl aromatic monomer in said (B)blocks; and f. the mol percent of vinyl aromatic monomers which areunsubstituted styrene monomers, ortho-substituted styrene monomers,meta-substituted styrene monomers, alpha-methylstyrene,1,1-diphenylethylene and 1,2-diphenylethylene in each (B) block beingbetween 10 mol percent and 100 mol percent.

In other embodiments, the sulfonated copolymer comprises a triblockcopolymer in which the end blocks (B) are comprised of arylene-vinylpolymer segments and the central block (A) is comprised of a dienepolymer segment comprising repeat units of at least four carbon atoms.In certain instances, the (B) blocks are susceptible to sulfonation andthe (A) blocks are resistant to sulfonation. In some cases, thearyl-containing sulfonated copolymer is an arylene-vinyl containingcopolymer prepared by anionic polymerization, or cationicpolymerization.

In certain embodiments, the sulfonated arylene-vinyl containingcopolymer comprises a hydrogenated central block. In some cases, thesulfonated arylene-vinyl containing copolymer is prepared by cationicpolymerization and comprises a saturated central block. In someembodiments, the sulfonated block copolymer is a triblock copolymer(A-B-A) in which the end blocks are comprised of arylene-vinyl polymerand the central block is comprised of a monoalkene polymer comprisingrepeat units of at least four carbon atoms. In other embodiments, thesulfonated copolymer is a pseudo-random block copolymer in which the endblocks are comprised of arylene-vinyl polymer and the central block iscomprised of a diene polymer comprising repeat units of at least fourcarbon atoms. In particular embodiments, the sulfonated copolymer is arandom block copolymer in which the end blocks are comprised ofarylene-vinyl polymer and the central block is comprised of a dienepolymer comprising repeat units of at least four carbon atoms.

In certain embodiments, the sulfonated copolymer is a random copolymercomprising an arylene-vinyl monomer and a non-arylene-vinyl comonomer.In other embodiments, the sulfonated copolymer is an aryl-containingcondensation polymer. The condensation copolymer may comprise apolyurethane, a polyamide, a polyester; a polysiloxane, or apolycarbonate.

In some embodiments, the sulfonated copolymer may have the generalconfiguration A-D-B-D-A, A-B-D-B-A, (A-D-B)_(n)X, (A-B-D)_(n)X, ormixtures thereof, where n is an integer from 2 to about 30, and X iscoupling agent residue wherein: a. each A block and each D block is apolymer block resistant to sulfonation and each B block is a polymerblock susceptible to sulfonation, said A, B and D blocks containing nosignificant levels of olefinic unsaturation; b. each A blockindependently having a number average molecular weight between 1,000 and60,000 and each B block independently having a number average molecularweight between 2,000 and 300,000; c. each A block comprising one or moresegments selected from polymerized (i) para-substituted styrenemonomers, (ii) ethylene, (iii) alpha olefins of 3 to 18 carbon atoms;(iv) 1,3-cyclodiene monomers, (v) monomers of conjugated dienes having avinyl, content less than 35 mol percent prior to hydrogenation, (vi)acrylic esters, (vii) methacrylic esters, and (viii) mixtures thereof,wherein any segments containing polymerized 1,3-cyclodiene or conjugateddienes are subsequently hydrogenated; d. each B block comprisingsegments of one or more vinyl aromatic monomers selected frompolymerized (i) unsubstituted styrene monomers, (ii) ortho-substitutedstyrene monomers, (iii) meta-substituted styrene monomers, (iv)alpha-methylstyrene, (v) 1,1-diphenylethylene, (vi) 1,2-diphenylethyleneand (vii) mixtures thereof; e. each D block comprises polymers having aglass transition temperature less than 20° C. and a number averagemolecular weight of between 1,000 and 50,000, said D block beingselected from the group consisting of (i) a polymerized or copolymerizedconjugated diene selected from isoprene, 1,3-butadiene having a vinylcontent prior to hydrogenation of between 20 and 80 mol percent, (ii) apolymerized acrylate monomer, (iii) a silicon polymer, (iv) polymerizedisobutylene and (v) mixtures thereof, wherein any segments containingpolymerized 1,3-butadiene or isoprene are subsequently hydrogenated; fsaid B blocks are sulfonated to the extent of 10 to 100 mol percent,based on the units of vinyl aromatic monomer in said B blocks; and g.the mol percent of vinyl aromatic monomers which are unsubstitutedstyrene monomers, ortho-substituted styrene monomers, meta-substitutedstyrene monomers, alpha-methylstyrene, 1,1-diphenylethylene and1,2-diphenylethylene in each B block being between 10 mol percent and100 mol percent.

In other embodiments, the sulfonated block copolymer comprises at leastone A block comprising polymers of one or more para-substituted styrenemonomers selected from para-methylstyrene, para-ethylstyrene,para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene,para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene,isomers of para-decylstyrene, and isomers of para-dodecylstyrene. Thesulfonated block copolymer A block may be a polymer block ofpara-t-butylstyrene and said B block is a polymer block of unsubstitutedstyrene. Alternatively, the A block is a polymer block ofpara-methylstyrene and said B block is a polymer block of unsubstitutedstyrene.

In some embodiments, the sulfonated block copolymer contains a D blockprior to hydrogenation wherein the D block is a polymer block of1,3-butadiene, and wherein 20 to 80 mol percent of the condensedbutadiene units in block D have 1,2-configuration prior tohydrogenation. In particular instances, the sulfonated block copolymermay be formed into articles that are insoluble in water and have thegeneral configurations A-B-A, A-B-A-B-A, (A-B-A)_(n)X, (A-B)_(n)X ormixtures thereof, where n is an integer from 2 to about 30, and X iscoupling agent residue and each A block is a polymer block resistant tosulfonation and each B block is a polymer block susceptible tosulfonation, said A and B blocks containing no significant levels ofolefinic unsaturation, wherein: a. each A block comprising one or moresegments selected from polymerized (i) para-substituted styrenemonomers, (ii) ethylene, (iii) alpha olefins of 3 to 18 carbon atoms;(iv) 1,3-cyclodiene monomers, (v) monomers of conjugated dienes having avinyl content less than 35 mol percent prior to hydrogenation, acrylicesters, (vii) methacrylic esters, and (viii) mixtures thereof, whereinany segments containing polymerized 1,3-cyclodiene or polymerizedconjugated dienes are subsequently hydrogenated and wherein any A blockcomprising polymerized ethylene or hydrogenated polymers of aconjugated, acyclic diene have a melting point greater than 50° C.; b.each B block is a copolymer block of at least one conjugated diene andat least one mono alkenyl arene selected from (i) unsubstituted styrenemonomers, (ii) ortho-substituted styrene monomers, (iii)meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v)1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixturesthereof, wherein said B block is subsequently hydrogenated; c. each Ablock having a number average molecular weight between 1,000 and 60,000and each B block having a number average molecular weight between 10,000and 300,000; d. the weight percent of mono alkenyl arene in each B blockbeing between 5 percent and 100 percent; e. the total amount of monoalkenyl arene in the sulfonated block copolymer being 20 percent weightto 80 percent weight; and f. said B blocks are sulfonated to the extentof 10 to 100 mol percent, based on the units of vinyl aromatic monomerin said B blocks.

In some embodiments, the sulfonated copolymer comprises apolyethersulfone, a polyetherketone, a methylmethacrylate, a triblock,such as a styrene-isobutylene-styrene, or an A block comprising polymersof one or more para-substituted styrene monomers selected frompara-methylstyrene, para-ethylstyrene, para-n-propylstyrene,para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene,para-iso-butylstyrene, para-t-butylstyrene, isomers ofpara-decylstyrene, and isomers of para-dodecylstyrene.

In some embodiments, the sulfonated triblock copolymer contains a Bblock comprising polymers of one or more alkylene monomers selected fromvariations of isobutylene, methyl cyclohexene, methylcyclopentene,1-methyl, 1′-ethyl ethane (and higher alkyl derivatives). In someembodiments, the copolymer comprises polyester (polylactides,polyglycolides, lactide-glycolide copolymers, terephthalate, and thelike).

The sulfonated polymers and the blends disclosed herein may be used in avariety of industrial settings and for a variety of applications. One ofskill in the art could adapt or modify the sulfonated polymers and thesubsequent blends described herein in order to be included in a varietyof applications. Further embodiments of the present invention includeprocesses for manufacturing various articles or compositions byutilizing the sulfonated polymers and/or blends described herein.

One of skill in the art would fully appreciate that the various articlesmay be further processed or have any number of other components present,including other sulfonated polymers or unsulfonated polymers. Forexample, certain articles may comprise a therapeutic or other agentincluding but not limited to antimicrobial agents (such asantibacterial, antifungal, antiviral—including inhibiting HumanImmunodeficiency Virus and Herpes Simplex Virus, spermicide,antiparasitic or other agent), anesthetics, growth factors,anti-inflammatory agents, antihistamines, analgesics, anti-neoplasticagents, hormones, tranquilizers, metals, vitamins, minerals, aminoacids, nucleic acids, cytokines, and the like). In certain embodiments,such as for use of the sulfonated polymers as membranes, it may benecessary that any such additive be miscible with the sulfonatedpolymer, not compromise the mechanical strength or integrity of themembrane, and/or not reduce the moisture transfer of the membrane.

Thus, for certain embodiments, the sulfonated polymers and/or blends maybe molded, dipped, fiber spun, extruded or otherwise processed intoarticles. The articles may take the form of a film, sheet, coating,band, strip, profile, molding, foam, tape, fabric, thread, filament,ribbon, bead (including microbeads and nanobeads), other spheres(including microspheres and nanospheres), knit, weave, fiber, pluralityof fibers, fibrous web, or any combination thereof. Any of these formsmay be solid, perforated, laminated, woven, non-woven, porous,non-porous, or the like and any combination thereof. In addition, thesulfonated polymers and/or blends may be utilized in various durable orconsumable goods.

For example, the sulfonated polymers and/or blends disclosed may be usedin various forms in the textile industry (such as for spinning fibers,fabrics, or polymeric blends); or in leather tanning (for example, forcoating leather articles). The sulfonated polymers and/or blends may becombined with any natural or synthetic fabric, including but not limitedto polyester fabric, poly(ethylene terephthalate) fabric, rayon fabric,acrylic fabric, polymeric fabric, cotton, jute, silk, wool, linen,twill, toile, bunting, duck, faille, gabardine, herringbone, jacquard,muslin, lawn, leno, paper or plant based fabrics, or others. Someexamples of articles that may be manufactured from the sulfonatedpolymers and their blends include clothing (including but not limited toshirts, jackets, pants, shoes, boots, socks, hats, bodysuits, gloves,head coverings, hazardous material protective clothing, gas and liquidfilters, tarps & drapes, including surgical drapes, goggles, etc.),blankets, rugs, furniture, carpeting, other floor coverings, and thelike.

Additionally, the sulfonated polymer and/or blend materials can be usedwhere one or more properties are desired, such as good materialcompatibility, good wet adhesion, good wet strength, adjustable waterabsorption, good water and proton transport characteristics, goodbiocompatibility, facile processing (such as easy film or membraneformation), adjustable drug-matrix properties, adjustable barrierproperties, adjustable flexibility and elasticity, adjustable hardness,and adjustable biological activity.

Specifically, in certain embodiments, the sulfonated polymer and/orblended materials may be adapted for use in surgery or other articlesrelated to medical intervention for diagnosis, treatment, or preventionof disease or a biological disorder. For example, tissue engineering;artificial neuron fibers; medical or dental cement; drug deliveryformulations; pharmaceutical compositions; implantable medical devicessuch as stents, catheters, cannulae, tubing (such as dialysis tubing),drug delivery patches, surgical repair patches, shunts, vascular grafts,artificial organ surfaces (such as heart, kidney, liver, pancreas, orother organ), heart valves, pacemakers, kidney dialysis, implants,artificial joints, intrauterine devices, microspherical particles forembolic therapy and/or drug delivery, contact lenses, assist devicesurfaces, including prostheses, or various other implantable devices orsurfaces, wound dressings (such as gauze dressings, bandages, sutures,and the like).

In certain embodiments, the sulfonated polymer and/or blended materialsdisclosed herein may be adapted to for use as equipment coatings;coatings for medical devices (such as biosensors, electrodes includingiontophoretic drug delivery patches, stent grafts, heart assists, etc.),adhesives, fluid absorbing materials, water gels, including bodily-fluidabsorbing materials (such as internal or external pads, tampons or othermaterial for use as for wounds, disposable diapers, urinary incontinenceproducts, feminine hygiene products, lactation or nursing products, andthe like); IV bags, blood bags, medical articles, such as hospitalgowns, laboratory wipe, surgical drapes, bedding, protective scrubs orclothing; coatings on tables; countertops; floors; or laboratoryequipment, etc.

In certain embodiments, the absorbent articles comprising the sulfonatedpolymer and or blended materials described herein may be neutralizedwith ammonia in order to provide protection against bacterial growth andrelated odor. Such super absorbent materials may be mixed in a fibrousmatrix, such as wood pulp. Super absorbent particles and materialscomprising the sulfonated polymer and/or blended materials describedherein would generally have an absorbent capacity of at least about 6grams of liquid per gram of fluff, or at least about 10 grams of liquidabsorbance, or at least about 20 grams of liquid absorbance, or at leastabout 40 grams of liquid absorbance. In some embodiments, the sulfonatedcopolymer may be left in its acid form so as to absorb putrid aminocompounds (that are liberated in the breakdown of amino acids andproteins) and may be useful where ammonia production is high.

In certain embodiments, the blends incorporating sulfonated polymersdisclosed herein may be utilized as matrices for oral pharmaceuticalformulations, suppositories, vaginal inserts, condoms, and other medicaldevices.

Due to the improved properties of the membranes resulting from blendsincorporating sulfonated polymers, such as the ability to be processedand formed without degradation, the membranes may also be utilized asair filters, medical clothing (such as in human and veterinary medicalfacilities), where protective clothing and breathable fabrics arenecessary. Further, the membranes, coated fabrics, fabric laminates, andfabrics created from spun fibers could provide a barrier of protectionfrom various environmental elements (wind, rain, snow, chemical orbiological organisms and agents) while offering a level of comfort as aresult of their ability to rapidly transfer water from one side of themembrane or fabric to the other. Thus, in certain instances moisturefrom perspiration can escape from the surface of the skin and fullenclosure suits fashioned from the membranes and fabrics can provideprotection to responders at emergency situations where smoke, chemicalspills, or various chemical or biological agents are a possibility.

The polymer blends incorporating sulfonated polymers disclosed hereinmay further be used in various applications in occupational safety orhomeland security, including polymer electrolyte membranes (PEMs) forchemical or biological protection clothing, instruments or otherarticles; fluid treatment (for example, membranes for fluid or gastreatment including desalination or other filtration of water,filtration of blood or other bodily fluids, filtration of food orbeverages, filtration of indoor or outdoor air, etc.), and the like.

Certain other embodiments relate to utilizing the sulfonated polymermembrane blends described herein for use with environmental controlelements (such as for heating, ventilating, air conditioning, cooling,humidity control, air filtration, etc.), and may include membranes,sensors, gauges, unitary humidity exchange cell (HUX), and the like.

The homogeneity of the sulfonated polymers disclosed herein make theseproducts and processes particularly suitable for producing membranes forapplications that require a high degree of uniform properties.Furthermore, the disclosed processes yield sulfonated polymers with alower level of conversion to get the useful sulfonated polymer. Thus, inone example, the sulfonated polymers may be used to form ion conductingmembranes, such as when cast from high dielectric constant solvents andare insoluble in water.

The sulfonated copolymers used for certain blends and resultingmembranes disclosed herein are preferably water-insoluble (having asolubility of less than 0.5 grams of polymer in 100 grams of water at100° C.).

In other embodiments, the polymeric blends described herein may be usedas marine or other coatings to prevent fouling in a moist environment,such as high humidity or aqueous immersion. The hydrophilic and anionicnature of the sulfonated polymeric blend materials would serve toprevent attachment of any variety of microorganisms, including bacteria,algae, plants, mollusks, and others.

Sulfonated copolymers, as used in polymer electrolyte membranes,generally exhibit good electrical conductivity (J. Electrochem. Soc.,142: L21-L23 (1995)), low methanol crossover rate (J. Electrochem. Soc.,143: 1233-1239 (1996)); excellent thermal stability (J. Electrochem.Soc. 143: 1225-1232 (1996)); very low or nearly zero water dragcoefficient (J. Electrochem. Soc. 143: 1260-1263 (1996)); as well asenhanced activity for oxygen reduction (J. Electrochem. Soc. 144:2973-2982 (1997)). Accordingly, certain sulfonated polymers disclosedherein may be useful as polymer electrolyte membranes.

In certain other embodiments, the sulfonated copolymers and their blendsdisclosed herein may be adapted for use in the electronics field, suchas for electrochemical devices (including membranes for fuel cells orfuel devices, and batteries); in testing assays or sensors (includingbiosensors, microfluidic devices, cell impedance sensors, moistureand/or heat transfer membranes, semiconductor chips or other computerparts, ultra-capacitors, other capacitors, other electronic sensors, orthe like). Certain such embodiments are taught in U.S. Pat. Nos.5,679,482; 5,468,574, 6,110,616, 6,413,298; and 6,383,391, which ishereby incorporated by reference in its entirety.

A fuel cell device generates electricity directly from a fuel source,such as hydrogen gas, and an oxidant, such as oxygen or air. A fuel celltypically comprises of two catalytic electrodes separated by anion-conducting membrane. The fuel gas (e.g. hydrogen) is ionized on oneelectrode, and the hydrogen ions diffuse across the membrane torecombine with the oxygen ions on the surface of the other electrode. Ifcurrent is not allowed to run from one electrode to the other, apotential gradient is built up to stop the diffusion of the hydrogenions. Allowing some current to flow from one electrode to the otherthrough an external load produces power.

In certain embodiments, the membrane made from the sulfonated moleculesdisclosed herein, is mechanically stable, allows the diffusion of ionsfrom one electrode to the other while preventing the flow of electrons,and/or keeps the fuel and oxidant gases apart. Diffusion or leakage ofthe fuel or oxidant gases across the membrane leads to explosions orother undesirable consequences.

Certain other embodiments relate to utilizing the sulfonated moleculesdescribed herein for use with environmental control elements (such asfor heating, ventilating, air conditioning, cooling, humidity control,etc.), and may include membranes, sensors, gauges, unitary humidityexchange cell (HUX), and the like.

The homogeneity of the sulfonated molecules disclosed herein make theseproducts and processes particularly suitable for producing membranes forapplications that require a high degree of uniformity of properties.Furthermore, the disclosed processes yield sulfonated molecules with alower level of conversion to get the useful sulfonated molecule. Thus,in one example, the sulfonated molecules may be used to form ionconducting membranes, such as when cast from high dielectric constantsolvents and are insoluble in water.

The sulfonated copolymers used for certain membranes, including thoseblended systems, disclosed herein are preferably water-insoluble (havinga solubility of less than 0.5 grams of polymer in 100 grams of water at100° C.).

For example, HUX cells may comprise a membrane that is utilized fortransferring water or other polar liquids or gases (including vapors)from one side of the cell to the other side of the cell by action of adifference in some quantity or gradient across the cell. This transferof water or gas may or may not be accompanied by evaporation of thewater or gas into or from the stream by the absorption of heat ordiabatic means. The membrane gradient may be produced by vapor pressure,osmotic or hydrostatic pressure, chemical, thermochemical,electrochemical, magnetochemical potential difference, or thermal,electric, electromagnetic, thermoelectric, or electrothermal potentialdifference. Examples of applications of HUX include but are not limitedto pervaporation, humidification and dehumidification of fuel cellstreams in stacks and devices, drying gases at pressure, tertiary oilrecovery, process control for synthetic manufacture of chemicals forwhich water is a reactant, isolation of minerals from mining fluids,industrial separation of oil-water emulsions, microfiltration andultrafiltration of colloidal suspensions and biological or organicmacromolecules for purification, maintaining water content of methanolin direct methanol fuel cells, reverse osmosis for isolation of freshwater from brine, electrolysis cells, dialysis, electro-dialysis,piezo-dialysis, electro-osmosis and chloro-alkali cells.

Still other embodiments relate to adapting the sulfonated macromoleculeor their blends disclosed herein for use as immersion coatings (such asfor marine paints and coatings); other coatings (such as for dragreduction for cars, boats, aircraft, motorcycles or other motorizedvehicles); consumable products (such as consumer electronics,appliances, toys, furniture, or packing materials); food and beverageindustry (for example for cartons, containers, packaging, jars, boxes,food wrapping, or the like); outdoor articles (such as tents, soilcoverings, tarps, recreational equipment, boating gear, lifevests, andthe like); building materials or other composites, as well as otherapplications.

EXAMPLES

The following examples are meant to be representative only, and notlimiting in any way.

Example 1 Blending SSIBS with TPU

Sulfonated Styrene-Isobutylene-Styrene (SSIBS) polymer solution (9 to15% solid) were prepared. SSIBS product varied in sulfonation levelsfrom 30 to 65 mol %.

Thermoplastic Polyurethane (TPU) (medical grade, Noveon) solutions wereprepared (9% solid) by dissolving the TPU in tetrahydrofuran (THF) andwere utilized to blend with the SSIBS solutions. The TPUs utilized were:

1. Tecophilic® hydrophilic aliphatic polyether-based TPU (high moistureabsorption).2. Tecoflex® aliphatic polyether-based TPU.3. Carbothane® aliphatic polycarbonate-based polyurethane.4. Tecoplast® aromatic polyether-based TPU.

Bionate®polycarbonate urethane from the Polymer Technology Group, Inc.was also prepared (6.7% solid) by dissolving in DMAC(N,N-dimethylacetamide).

The following polymer blends were produced utilizing the aboveconstituents:

A. Blend 56 mol % SSIBS/Tecophilic® in 50/50 by weight: Tecophilic®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (10g, 10% solids, 56 mol % sulfonation) by way of pipette while stirring,and continuous stirring overnight at 40° C. A clear solution resultedand a clear, transparent membrane was obtained following casting.B. Blend 56 mol % SSIBS/Tecoflex® in 50/50 by weight: Tecoflex®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (10g, 10% solids, 56 mot % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A clear solution resulted anda clear, transparent membrane was obtained following casting.C. Blend 56 mol % SSIBS/Carbothane® in 50/50 by weight: Carbothane®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (10g, 10% solids, 56 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A homogenous solution wasobtained and a clear, transparent membrane was obtained followingcasting.D. Blend 52 mol % SSIBS/Tecoplast® in 50/50 by weight: Tecoplast®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (8 g,12.6% solids, 52 mol % sulfonation) by way of pipette while stirring andcontinual stirring overnight at 40° C. A homogenous solution wasobtained and a clear, transparent membrane was obtained followingcasting.E. Blend 52 mol % SSIBS/Tecophilic® in 75/25 by weight: Tecophilic®/THFsolution (22 g, 9% solids) was added to the SSIBS polymer solution (40g, 15% solids, 52 mol % sulfonation) by way of pipette while stirring,and continual stirring overnight at 40° C. A clear solution resulted anda clear, transparent membrane was obtained following casting.F. Blend 52 mol % SSIBS/Tecoflex® in 75/25 by weight: Tecoflex®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (20g, 15% solids, 52 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A clear solution resulted anda clear, transparent membrane was obtained following casting.G. Blend 52 mol % SSIBS/Carbothane® in 75/25 by weight: Carbothane®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (23.8g, 12.6% solids, 52 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A homogenous solutionresulted and a clear, transparent membrane was obtained followingcasting.H. Blend 40 mol. % SSIBS/Tecophilic® in 50/50 by weight: Tecophilic®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (8.7g, 11.5% solids, 40 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A homogenous solutionresulted and a clear, transparent membrane was obtained followingcasting.I. Blend 40 mol % SSIBS/Tecoflex® in 50/50 by weight: Tecoflex®/THFsolution (11 g, 9% solids) was added to the SSIBS polymer solution (8.7g, 11.5% solids, 40 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A homogenous solutionresulted and a clear, transparent membrane was obtained followingcasting.J. Blend 50 mol % SSIBS/Bionate® in 50/50 by weight: Bionate®/DMACsolution (54 g, 61% solids) was added to the SSIBS polymer solution (24g, 15% solids, 50 mol % sulfonation) by way of pipette while stirringand continual ing overnight at 40° C. A homogenous solution resulted anda clear, transparent membrane was obtained following casting.

Example 2 Blending SSIBS with Silicon Urethane Copolymers

SSIBS polymer solutions (9 to 15% solids) were prepared with varyingsulfonation levels (30-65 mol %). Two silicone urethane copolymers(PurSil™ and CarboSil™ from the Polymer Technology Group, Inc, wereutilized in the experiments. PurSil™ is a silicone polyether urethaneand CarboSil™ is a silicone polycarbonate urethane.

The silicone urethane copolymer/DMAC solutions (7 to 9%) were preparedby dissolving the polymer resin in DMAC. The following blends wereprepared: (Note: THF can be used as well as the solvent)

a. Blend: 50 Mol % SSIBS/PurSil™ 50/50 by weight: PurSil™/DMAC solution(44 g, 9% solids) was added to the SSIBS polymer solution (31.7 g,12.6.% solids, 50 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A homogenous solutionresulted and a clear, transparent membrane was obtained followingcasting.b. Blend: 50 mol % SSIBS/CarboSil™ 50/50 by weight: CarboSil™/DMACsolution (57 g, 7% solids) was added to the SSIBS polymer solution (27g, 15% solids, 50 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A homogenous solutionresulted and a clear, transparent membrane was obtained followingcasting.c. Blend: 50 mol % SSIBS/PurSil™ 75/25 by weight: PurSil™/DMAC solution(22 g, 9% solids) was added to the SSIBS polymer solution (57 g, 10.5%solids, 51 mol % sulfonation) by way of pipette while stirring andcontinual stirring overnight at 40° C. A homogenous solution resultedand a clear, transparent membrane was obtained following casting.d. Blend: 50 mol % SSIBS/CarboSil™ 75/25 by weight: CarboSil™/DMACsolution (28.6 g, 7% solids) was added to the SSIBS polymer solution (57g, 10.5% solids, 51 mol % sulfonation) by way of pipette while stirringand continual stirring overnight at 40° C. A homogenous solutionresulted and a clear, transparent membrane was obtained followingcasting.

Example 3 Cast Membrane of Blend SSIBS with TPUs and SSIBS with SiliconeUrethane Copolymers

The above polymer blended solutions were slot cast onto silicone-coatedpolyester release liners on heated vacuum assisted casting tables withdifferent blade settings. Membranes of different thickness resulted. Themembranes were dried to remove solvent in a lab fume hood.

The prepared membranes were evaluated using a routine moisture transfertest based on DI water uptake at room temperature for 3 and 24 hours aswell as total mass (moisture & ion) uptake in 0.9% saline solution at50° C. for 3 and 24 hours. The results of these tests are detailed inTable 1.

TABLE 1 SSIBS-Polyurethane total water absorbance data (0.9% saline, 50°C.) % mass uptake Formulation @ 3 hours 56 mol % SO₃H SSIBS 187 56 mol %SO₃H SSIBS:Tecophilic ® (50:50) 153 56 mol % SO₃H SSIBS:Tecoflex ®(50:50) 174 56 mol % SO₃H SSIBS:Carbothane ® (50:50) 123 56 mol % SO₃HSSIBS:Tecoplast ® (OP) (50:50) 110 56 mol % SO₃H SSIBS:Tecoplast ® (TP)(50:50) 97.7 56 mol % SSIBS:PureSil ® (50:50) 54 56 mol %SSIBS:CarboSil ® (50:50) 62

Example 4 Laminate Preparations from Blended Membranes

Two types of laminated samples were prepared. The first type of samplewas assembled by preparing a sandwich of two layers (4×4 inch, orapproximately 10.16 cm×10.16 cm) of Tegapore™ material (3M, Minneapolis,Minn.) with the blended membrane (4×4 inch, or approximately 10.16cm×10.16 cm). This tri-layer membrane sandwich was then laminated at atemperature range of approximately 80-120° C.

The second type of sample was assembled by cutting Tegapore™ materialinto two exact sizes of frame shape with an overhanging edge ofapproximately 0.5 inches (1.27 cm) and assembling the blended membranewith the two frame shaped Tegapore™ material and then laminating themtogether at a temperature range of approximately 80-120° C.

Example 5 Conversion of the Laminated Samples into the Sodium Form

The laminated membrane samples were immersed in sodium bicarbonate(aqueous solution of approximately 3%) at room temperature for 15minutes. The membranes were then removed from the solution, excesssolution was removed by shaking the membranes, and the membranes wereset on paper towels to dry, thereby producing the sodium form of thelaminated membrane samples.

The sodium form of the laminated membrane samples were then treated withdoxycycline by immersing the sodium form of the laminated membranesamples in doxycycline (aqueous solution, 1 g of doxycycline in 1 Ldeionized water) at room temperature for 15 minutes. The membranes werethen removed from the doxycycline solution, excess solution was removedby shaking the membranes, and the membranes were set on paper towels todry. The release of doxycycline tracks water absorbance with theSSIBS:SIBS blend showing release out beyond 72 hours. The results ofthis water absorbance are shown in Table 2. As can be seen, the wetmechanical properties of the sulfonated polymer membranes increased, andadhesion to stainless steel and glass improved as the SIBS componentincreased.

TABLE 2 SSIBS-SIBS water absorbance data Formulation 2 h 3 h 24 h 48 h72 h 56 Mol %  26%  33%  34%  40%  43% SSIBS:SIBS (50/50) 56 Mol %  13% 26%  31%  39%  44% SSIBS:SIBS (60/40) 56 Mol % 114% 116% 124% 131% 135%SSIBS:SIBS 75/25 56 Mol % 153% 187% 199% 203% 206% SSIBS:SIBS 90/10

Example 6 Modified Sulfonated Styrene Block Copolymers for VascularApplications

We have prepared sulfonated polymeric blends as described herein toproduce blended materials of sulfonated SIBS (block copolymers) combinedwith polyurethane (such as polycarbonate urethane, polysiloxy urethane,and polyether urethane) as well as sulfonated SIBS. The membrane filmswere prepared by solvent casting onto siliconized release liner, or aPTFE sheet. We have characterized the saline water absorbancecharacteristics of these materials as well as their ability to release(retain) a water soluble drug (Doxycycline) that binds to the sulfonategroup of the polymer, and the ability of these blended materials todeter the attachment of platelets under static conditions.

In platelet adhesion studies, 16 mm diameter discs of SSIBS (56 mol %)were cut from solvent cast films of 50:50 SSIBS:SIBS using a cork-borerand the cut films were placed in well plates, washed and incubated withPBS (phosphate buffered solution) overnight. Next, the discs wereexposed to human platelet rich plasma for one hour, washed with PBS, andstained with FITC-anti-CD41a. Finally, the discs were fixed with 4%paraformaldehyde and imaged using an epifluorescent microscope at 40×.PTFE control samples were prepared in the same fasion, exposed toplatelet rich plasma, fixed, and imaged in parallel.

SSIBS (56 mol % sulfonation) blended with the non-sulfonated SIBSpolymer in a ratio of 50:50 w/w with SSIBS in its acid form and in itssodium salt form as prepared by exposure to 0.9% normal saline (ionexchange) showed very high levels of resistance to platelet adhesion andvery little platelet aggregation relative to the control PTFE sample,and were comparable to negative controls such as albumin coatedsurfaces. Further, the platelets that attached to these surfaces did notappear to be activated to any significant degree as evidenced by a lackof spreading pseudopods. Results are shown in FIGS. 2-4.

Doxycycline release from the same 50:50 blend of SSIBS:SIBS/Na+ form(following incorporation by 10 minute exposure to 0.1M aqueousDoxycycline:HCl) was produced from a thin film over a 72 hour period in37° C. PBS. At 72 hours the doxycycline is still present in the sample,but is approaching equilibrium (FIG. 1). Thus, the membranes describedherein can bind cations and retain cations for extended time periodsthat will allow for use with endothelial cell attachment. Othermembranes tested included SB3T-30/56-024/SIBS (60:40)-Na+,Carbosil™/SSEBS (50:50), and SBT-30/40-013 Teco (50:50). Furthermore,co-spraying a SSIBS lacquer simultaneously with a SIBS-peptide laquer isbelieved to yield improved incorporation into the material.

Studies conducted with the same polymer blends and PE-anti-CD62P (anti-Pselectin) (Invitrogen) staining provided similar results with regard toanti-thrombotic characteristics of the polymer blend materials tested.

Example 7 Capillary Rheometry Results

The thermal processing characteristics, such as shear viscosity rates,of several exemplary sulfonated polymer blend membranes were tested bycapillary rheometry. Generally, sulfonated polymers, particularly intheir acid forms, are not stable to temperatures necessary to thermallyprocess into sheet, film, rod, tube, or complex form by way of transfermolding, injection molding, press molding, extrusion or the like. Thisis because desulfonation (and subsequent liberation of SO₃) leads todecomposition and charring. In addition, block polymers in some casesare not amenable to extrusion or transfer molding due to the high meltviscosities of these materials.

Briefly, each blend sample was test extruded through a die of defineddimension, and the shear pressure drop across the die was recorded at aset volumetric flow rate. The pressure drop was measured as each samplebeing tested was extruded through the die.

In this particular Example, a Dynisco LCR 7001 Capillary Rheometer wasutilized with a die dimension of 20 mm length by 1 mm diameter (180°entrance angle). Predrying was accomplished using a vacuum oven at 70°C. for 4 hours. Sensor 1 force values indicate the load cell readings inNewtons (N), where values less than 100N are below the sensitivity ofthe load cell. Results are shown in Tables 3 and 4, and also representedin FIGS. 5 and 6, respectively,

TABLE 3 TecoFlex EG80A/SSIBS Blend (70:30), Temperature of 177° C.,Shear Rates of 2000 to 25 sec⁻¹, melt time of 360 seconds Sensor Posi-Shear Shear Shear Force tion RamRate Time Stress Rate Viscosity Point(N) (mm) (mm/min) (min) (kPa) (1/s) (Pa-s) 1 3429 132.8 164.8 6.20598.33 2004.55 298.49 2 2864 152.3 88.1 6.42 499.79 1071.90 466.27 32422 157.2 47.1 6.52 422.56 573.16 737.25 4 1988 162.3 25.2 6.73 348.65306.46 1137.66 5 1660 169 13.5 7.23 289.63 163.93 1766.77 6 1327 172.77.2 7.74 231.58 87.68 2641.09 7 1076 175.6 3.9 8.50 187.77 46.82 4010.378 858 177.3 2.1 9.32 149.64 25.05 5973.00 9 1910 183.2 25.2 9.55 333.34306.46 1087.68

TABLE 4 TecoFlex EG80A/SSIBS Blend (50:50), Temperature of 177° C.,Shear Rate of 2000 to 25 sec⁻¹, melt time of 360 seconds Sensor Posi-Shear Shear Shear Force tion RamRate Time Stress Rate Viscosity Point(N) (mm) (mm/min) (min) (kPa) (1/s) (Pa-s)  1* 6055 127.5 164.8 6.171056.55 2004.55 527.08 2 3238 189.5 88.1 6.87 565.07 1071.90 527.17 32815 193.8 47.1 6.97 491.16 573.16 856.92 4 2406 197.1 25.2 7.10 419.81306.46 1369.86 5 2017 201.6 13.5 7.43 352.00 163.93 2147.23 6 1697 203.87.2 7.73 296.19 87.68 3378.00 7 1431 205.8 3.9 8.25 249.70 46.82 5333.128 1218 207.1 2.1 8.87 212.53 25.05 8483.49 9 2218 220 25.2 9.39 337.03306.46 1262.90 *Point 1 is not valid due to the elasticity of thematerial. The material was forced down in the barrel but air was stillpresent through the beginning of the run. These data indicate twoimportant points: (1) The materials that were tested both melted andextruded from the barrel with the demonstrated formation of a continuousrod of the blend material, and (2) the extruded material did not revealany discoloration indicating that the sulfonated material has notundergone any sulfonation.

All of the above U.S. patents, U.S., patent application publications,U.S. patent applications, foreign patents, foreign patent applicationsand non-patent publications referred to in this specification and/orlisted in the Application Data Sheet, are incorporated herein byreference, in their entirety.

From the foregoing it will be appreciated that, although specembodiments of the invention have been described herein for purposes ofillustration, various modifications may be made without deviating fromthe spirit and scope of the invention. Accordingly, the invention is notlimited except as by the appended claims

1-41. (canceled)
 42. A polymeric material that is water insoluble andcomprises (i) at least one uniformly sulfonated aryl-containing blockcopolymer comprising at least one arene moiety-containing unit and atleast one non-arene moiety-containing unit, wherein said sulfonatedaryl-containing block copolymer is 30-80 mol % sulfonated; wherein saidsulfonated aryl-containing block copolymer comprises a random blockcopolymer, a triblock copolymer, or a pseudorandom block copolymerwherein the end blocks comprise arylene-vinyl polymer and the centralblocks comprise at least one hydrogenated segment prepared from a dieneselected from the group consisting of isoprene, butadiene,1-methyl-1-ethyl ethane, or higher alkylene derivatives thereof, and(ii) at least one thermoplastic or thermosetting non-sulfonatedhomopolymer or copolymer selected from the group consisting of apolyurethane, a segmented polyurethane, a poly(ether urethane), apoly(carbonate urethane), a poly(siloxy urethane), a polyurethane urea,an arylene-vinyl containing block copolymer, a polysiloxane, apolyamide, a polyketone, a polyester, a poly(ether-ester), apolyanhydride, a polyamine, a poly(ortho ester), a polyacrylate, apolyalkylene, a polycarbonate, a fluoropolymer, a polysulfone,carbohydrate polymers, a polypeptide, a polyphosphazine, a polyether, apoly(ether sulfone), a poly(vinylalcohol), poly(ethylene-co-vinylacetate), poly(ethylene-co-vinyl alcohol), a poly(epoxide)-polyaminecuring system, and an acrylate.
 43. The polymeric material of claim 42,wherein said uniformly sulfonated aryl-containing block copolymercomprises a pseudo-random block copolymer or a random block copolymerwherein the end blocks comprise arylene-vinyl polymer.
 44. The polymericmaterial of claim 42, wherein said uniformly sulfonated aryl-containingblock copolymer comprises polyethersulfone, polyetherketone,polystyrene, methylmethacrylate, polydioxanone, polylactides,polyglycolides, lactide-glycolide copolymers, or polyesters.
 45. Anarticle of manufacture made with the polymeric material of claim 42,wherein said article is selected from the group consisting of amembrane, a medical device, a pharmaceutical composition, a moisturetransfer membrane, a fluid-absorbing material, a fuel cell, a capacitor,a wound dressing, a fabric, a building material, a desalination membraneor device, a membrane for heating, a membrane or device for ventilatingand air conditioning (HVAC), a packing material, a surface coating, ashunt, a stent, tubing, clothing, bedding, surface coatings, fluidabsorbing materials, adhesives, fluid collection or storage bags,sensors, gauges, and fluid filters.
 46. A method of making the polymericmaterial of claim 42, wherein said method comprises the steps ofcombining at least one sulfonated polymer in solution with at least onenon-sulfonated polymer, allowing the solution to thoroughly mix, andisolating and/or processing the polymer blend.
 47. The method of claim46 wherein said step of isolating and/or processing the polymer blendcomprises at least one of spray drying, precipitation, solventevaporation, extruding, electrospraying, electrospinning, andprecipitating the polymer blend.
 48. The method of claim 46 furthercomprising the step of converting the polymer blend to salt form.
 49. Amethod of making an article of manufacture comprising the polymericmaterial of claim 42 comprising the steps of combining at least onesulfonated polymer in solution with at least one non-sulfonated polymer,allowing the solution to thoroughly mix, isolating the polymer blend,and manipulating the polymer blend to form the article.
 50. The methodof claim 49, wherein said step of manipulating the polymer blendcomprises at least one of thermal lamination, transfer molding, pressmolding, extruding, thermal fiber-spinning, electrospinning,electrospraying, painting, dipping, and pressure spraying.
 51. Apolymeric material that is water insoluble and comprises (i) at leastone sulfonated aryl-containing block copolymer comprising at least onearene moiety-containing unit and at least one non-arenemoiety-containing unit, wherein said sulfonated aryl-containing blockcopolymer is 30-80 mol % sulfonated; wherein the end blocks of saidsulfonated aryl-containing block copolymer comprise arylene-vinylpolymer and the central blocks of said sulfonated aryl-containing blockcopolymer comprise at least one hydrogenated segment prepared from adiene, and (ii) at least one thermoplastic or thermosettingnon-sulfonated homopolymer or copolymer selected from the groupconsisting of a polyurethane, a segmented polyurethane, a poly(etherurethane), a poly(carbonate urethane), a poly(siloxy urethane), apolyurethane urea, an arylene-vinyl containing block copolymer, apolysiloxane, a polyamide, a polyketone, a polyester, apoly(ether-ester), a polyanhydride, a polyamine, a poly(ortho ester), apolyacrylate, a polyalkylene, a polycarbonate, a fluoropolymer, apolysulfone, carbohydrate polymers, a polypeptide, a polyphosphazine, apolyether, a poly(ether sulfone), a poly(vinylalcohol),poly(ethylene-co-vinyl acetate), poly(ethylene-co-vinyl alcohol), apoly(epoxide)-polyamine curing system, and an acrylate.
 52. A polymericmaterial that is water insoluble and comprises (i) at least oneuniformly sulfonated aryl-containing block copolymer comprising at leastone arene moiety-containing unit and at least one non-arenemoiety-containing unit, wherein said sulfonated aryl-containing blockcopolymer is 30-80 mol % sulfonated; wherein said sulfonatedaryl-containing block copolymer comprises a random block copolymer, atriblock copolymer, or a pseudorandom block copolymer wherein the endblocks comprise arylene-vinyl polymer and the central blocks comprise atleast one monoalkene polymer segment prepared from a monoalkene selectedfrom the group consisting of isobutylene, methyl cyclohexene, andmethylcyclopentene, and (ii) at least one thermoplastic or thermosettingnon-sulfonated homopolymer or copolymer selected from the groupconsisting of a polyurethane, a segmented polyurethane, a poly(etherurethane), a poly(carbonate urethane), a poly(siloxy urethane), apolyurethane urea, an arylene-vinyl containing block copolymer, apolysiloxane, a polyamide, a polyketone, a polyester, apoly(ether-ester), a polyanhydride, a polyamine, a poly(ortho ester), apolyacrylate, a polyalkylene, a polycarbonate, a fluoropolymer, apolysulfone, carbohydrate polymers, a polypeptide, a polyphosphazine, apolyether, a poly(ether sulfone), a poly(vinylalcohol),poly(ethylene-co-vinyl acetate), poly(ethylene-co-vinyl alcohol), apoly(epoxide)-polyamine curing system, and an acrylate.